The title synthesized hypophosphite has the formula V(H(2)PO(2))(3). Its structure is based on VO(6) octahedra and (H(2)PO(2))(-) pseudo-tetrahedra. The asymmetric unit contains two crystallographically distinct V atoms and six independent (H(2)PO(2))(-) groups. The connection of the polyhedra generates [VPO(6)H(2)](6-) chains extended along a, b and c, leading to the first three-dimensional network of an anhydrous transition metal hypophosphite.