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William Still was born October 7, 1821 in Burlington County, New Jersey, to Sidney (later renamed Charity) and Levin Still. His parents had come to New Jersey from the Eastern Shore of Maryland. William was the youngest of eighteen siblings. His siblings included Dr. James Still (1812–84) known as "the Doctor of the Pines," Peter Still, Samuel Still, Mary Still, a teacher and missionary in the African Methodist Episcopal Church, Mahala Still (Mrs. Gabriel Thompson) and Kitturah Still, who moved to Pennsylvania.
William's father Levin was the first of the family to move to New Jersey. Born a slave, he had saved enough to purchase his freedom and had been manumitted in 1798 in Caroline County, Maryland. Levin eventually settled in Evesham near Medford. Levin's wife Charity, then a slave in Maryland, escaped with their four children. Charity and her children were recaptured and returned to slavery, but she escaped a second time and, with her two daughters, found her way to Burlington County to join her husband. The two sons she left behind, Levin Jr and Peter, were sold to slave-owners in Lexington, Kentucky, and then later, sent to Alabama in the Deep South. Following her escape to New Jersey Charity and Levin went on to have fourteen more children, of whom William was the youngest.
Levin Still, Jr. died while enslaved. Peter Still and his family were able to escape from slavery with the help of two brothers named Friedman, who operated mercantile establishments in Florence, Alabama and Cincinnati, Ohio. Peter Still's travails, and that of his family, were written about in Kate E. R. Pickard's 1856 book The Kidnapped and the Ransomed: Recollections of Peter Still and his Wife "Vina," After Forty Years of Slavery.
When Peter Still first sought William Still's help find the family members he (Peter) hadn't seen since the age of six he had no idea that William was his younger brother. Upon hearing Peter's story, William recognized the story his own mother had told many time and after hearing about his older brother Levin being whipped to death for visiting his wife without permission, William shouted, "What if I told you I was your brother!" Later Peter and his mother were able to meet after being separated for forty two years.
Another of William's brothers was Doctor James Still. James, who was born in 1812, wanted to become a doctor but, per his own description "was not the right color to enter where such knowledge was dispensed". James studied herbs and plants and apprenticed himself to white doctor to learn medicine. He became known as the "Black Doctor of the Pines". James' son, James Thomas Still, graduated from Harvard's School of Medicine in 1871.
In 1844, William Still moved to Philadelphia, Pennsylvania where, in 1847, he married Letitia George. William and Letitia had four children who survived infancy. Their oldest was Caroline Matilda Still (1848–1919), a pioneer female medical doctor. Caroline attended Oberlin College and the Women's Medical College of Philadelphia (much later the Medical College of Pennsylvania); she was married, first to Edward J. Wyley, and after his death, to the Reverend Matthew Anderson, longtime pastor of the Berean Presbyterian Church in North Philadelphia. She had an extensive private medical practice in Philadelphia and was also a community activist, teacher and leader. William Wilberforce Still (1854–1914) graduated from Lincoln University and subsequently practiced law in Philadelphia; Robert George Still (1861–1896), was a journalist who owned a print shop on Pine at 11th Street in central Philadelphia, and Frances Ellen Still (1857–1930) became a kindergarten teacher (she was named after poet Frances Ellen Watkins Harper, who lived with the Stills before her marriage). On the 1900 U.S. Census William Still said he had two children, William W. and Ellen, still living in his household, as well as a daughter-in-law. 
The three prominent Still brothers—William, James, and Peter—settled in Lawnside, New Jersey. To this day, their descendants have an annual family reunion every August. Notable members of the Still family include the composer William Grant Still, professional WNBA basketball player Valerie Still, professional NFL defensive end Art Still, and professional NFL defensive tackle Devon Still.
In 1847, three years after his arrival in Philadelphia, William Still began working as a clerk for the Pennsylvania Anti-Slavery Society. When Philadelphia abolitionists organized a committee to aid runaway slaves reaching Philadelphia, Still became its chairman. By the 1850s, Still was a leader of Philadelphia's African-American community. In 1859 he attempted to desegregate the city's public transit system. He opened a stove store during the American Civil War, operated the post exchange at Camp William Penn, the training camp for United States Colored Troops north of Philadelphia. After the war, Still owned and operated a coal delivery business.
Often called "The Father of the Underground Railroad", Still helped as many as 800 slaves escape to freedom, interviewing each person and keeping careful records, including a brief biography and the destination of each person, along with any alias that they adopted, though he kept his records carefully hidden. One of those escaped slaves who he helped was his own older brother Peter, whom he had never met. Still worked with other Underground Railroad agents operating in the south and in many counties in southern Pennsylvania. His network to freedom also included agents in New Jersey, New York, New England and Canada. Harriet Tubman traveled through his office with fellow passengers on several occasions during the 1850s. After the Civil War, Still published the secret notes he'd kept in diaries during those years, and his book is a source of many historical details of the workings of the Underground Railroad. He is one of the many who helped slaves escape from the southern United States.
Still also had a strong interest in the welfare of black youth. He helped to establish an orphanage for black youth and he also helped to organize the first YMCA for African-Americans in Philadelphia.