It was developed by Henri Sevene and Emile David Cahen in 1898 as part of their invention of friction matches that did not pose the health hazards of white phosphorus.

The compound was discovered by G. Lemoine and first produced safely in commercial quantities in 1898 by Albright and Wilson.

Unlike some other phosphorus sulfides, P4S3 is slow to hydrolyze and has a well-defined melting point.

[8] Exposure to "strike anywhere" matches containing phosphorus sesquisulfide can cause contact dermatitis, usually in the pocket area but also on the face.

[9] Exposure over a long period of time to burning match tips (containing phosphorus sesquisulfide) can result in a recurring severe primary dermatitis about the eyes and face.