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He was educated at the military school of Brienne in Champagne along with Napoleon Bonaparte; and although the solitary habits of the latter made intimacy difficult, the two youths seem to have been on friendly terms. However, the stories of their very close friendship, as told in Bourrienne's memoirs, are open to suspicion.
Leaving Brienne in 1787, and conceiving a distaste for the army, Bourrienne proceeded to Vienna. He was pursuing legal and diplomatic studies there, and afterwards at Leipzig, when the French Revolution broke out and went through its first phases. Not until the spring of 1792 did Bourrienne return to France; at Paris he renewed his acquaintance with Bonaparte. They led a Bohemian life together, and among other incidents of that exciting time, they witnessed the mobbing of the royal family in the Tuileries (June 20) and the overthrow of the Swiss Guards at the same spot (August 10).
Bourrienne next obtained a diplomatic appointment at Stuttgart, and soon his name was placed on the list of political émigrés, from which it was not removed until November 1797. Nevertheless, after the affair of 13th Vendémiaire (October 5, 1795) he returned to Paris and renewed his acquaintance with Bonaparte, who was then second in command of the Army of the Interior and soon received the command of the Army of Italy. Bourrienne did not proceed with him into Italy, but was called there by the victorious general at the time of the long negotiations with Austria (May–October 1797), when his knowledge of law and diplomacy was useful in drafting the terms of the Treaty of Campo Formio (October 7).
The following year he accompanied Bonaparte to Egypt as his private secretary, and left a vivid, if not very trustworthy, account of the expedition in his memoirs. He also accompanied him on the adventurous return voyage to Fréjus (September–October 1799), and was of some help in the affairs that led up to the coup d'état of Brumaire (November) 1799. He remained by the side of the First Consul in his former capacity, but in the autumn of 1802 incurred Bonaparte's displeasure, ostensibly because of questionable financial dealings.
In the spring of 1805 he was sent as French envoy to the free city of Hamburg. There it was his duty to carry out the measures of commercial war against England, known as the Continental System; but it is known that he not only viewed those tyrannical measures with disgust, but secretly relaxed them in favour of those merchants who plied him with douceurs. In the early spring of 1807, when directed by Napoleon to order a large number of military cloaks for the army, then in East Prussia, he found that the only means of procuring them expeditiously was to order them from England. After gaining a large fortune while at Hamburg, he was recalled to France in disgrace at the close of 1810.
In 1814 he embraced the royal cause, and during the Hundred Days (1815) accompanied Louis XVIII to Ghent. The rest of his life was uneventful; he died at Caen on February 7, 1834, after suffering from a mental malady for two years.
The fame of Bourrienne rests not upon his achievements or his original works, which are insignificant, but upon his Mémoires, edited by C. M. de Villemarest (10 vols., Paris, 1829-1831), which have been frequently republished and translated. The best English edition is that edited by Colonel R. W. Phipps (4 vols., London, 1893); a new French edition has been edited by D. Lacroix (5 vols., Paris, 1899-1900). See Bourrienne et ses erreurs, volontaires et involontaires (Paris, 1830), by Generals Belliard, Gourgaud, etc., for a discussion of the genuineness of his Memoirs; also Napoleon et ses détracteurs, by Prince Napoleon (Paris, 1887; Eng. trans., London, 1888).