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Born Maria de los Ángeles Gulín in Ribadavia, Spain, she moved with her family at the age of eight in Montevideo, Uruguay, where she studied singing with her father, who became a local music director who organized concerts in parks. She made her operatic debut there in 1963, as the Queen of the Night in The Magic Flute, as last minute replacement. She then returned to Europe where she sang mostly in Spain and Italy in roles such as Lucia in Lucia di Lammermoor, Gilda in Rigoletto and Violetta in La traviata.
After winning the Busseto Verdian Voices Competition in 1968, she turned to more dramatic roles and specialized in early Verdi works. Gulín's repertoire included Oberto, Nabucco, I due Foscari, Giovanna d'Arco, Attila, Alzira, Il corsaro, Luisa Miller, Stiffelio, Aroldo, I vespri siciliani, Simon Boccanegra, Un ballo in maschera, La forza del destino and Aida. Her repertoire also included roles in Rossini's La donna del lago, Bellini's Beatrice di Tenda and Norma, Spontini's Fernand Cortez, Meyerbeer's Les Huguenots, Ponchielli's La Gioconda, Rachmaninoff's Francesca da Rimini, de Falla's La vida breve, Giordano's Andrea Chénier and Puccini's Turandot.
Gulín's voice was rich and large, but capable of agility. Her career was cut short in 1987 due to serious health problems. She died in Madrid.
She was married to the baritone Antonio Blancas. Their daughter Ángeles Blancas Gulín is also a soprano.
She was rediscovered through the appearance of several recordings of her live performances.