The compound has been prepared in a multistep process starting with the base hydrolysis of phosphorus pentasulfide:
:PS  +  6 NaOH   →   2 NaPOS  +  HS  +  2 HO
The salt is isolated as the hydrate NaPOS(HO).  It is prone to hydrolysis, especially when it is heated as an aqueous solutions:
:NaPOS  +  2 HO   →   NaPOS  +  HS
Its structure has been examined by X-ray crystallography.