Facile and reproducible methods for the syntheses of bis(di-iso-propylselenophosphinyl)selenide ((i)Pr2PSe)2Se (1), bis(di-iso-propylselenophosphinyl)diselenide ((i)Pr2PSe)2Se2 (2) and bis(di-phenylselenophosphinyl)selenide (Ph2PSe)2Se (3) is reported.