Philippe Gengembre (1764–1838), a student of Lavoisier, first obtained phosphine in 1783 by heating white phosphorus in an aqueous solution of potash (potassium carbonate).
Perhaps because of its strong association with elemental phosphorus, phosphine was once regarded as a gaseous form of the element, but Lavoisier (1789) recognised it as a combination of phosphorus with hydrogen and described it as phosphure dhydrogène' (phosphide of hydrogen).
In 1844, Paul Thénard, son of the French chemist Louis Jacques Thénard, used a cold trap to separate diphosphine from phosphine that had been generated from calcium phosphide, thereby demonstrating that  is responsible for spontaneous flammability associated with , and also for the characteristic orange/brown color that can form on surfaces, which is a polymerisation product. He considered diphosphine's formula to be , and thus an intermediate between elemental phosphorus, the higher polymers, and phosphine. Calcium phosphide (nominally ) produces more  than other phosphides because of the preponderance of P-P bonds in the starting material.
The name "phosphine" was first used for organophosphorus compounds in 1857, being analogous to organic amines ().  The gas  was named "phosphine" by 1865 (or earlier).