Reaction of (PhPSe2)2(Woollins reagent) with NaOR (R = Me, Et, (i)Pr) gives the non-symmetric phosphonodiselenoato anions [Ph(RO)PSe2]- which can be complexed to a range of metals. The nickel complex Ni[Ph(MeO)PSe2]2 adopts a square-planar ML2 structure while the cadmium complex Cd[Ph(MeO)PSe2]2 displays a dimeric M2L4 structure. Two different lead complexes are observed, one consisting of PbL2 units joined by Pb...Se interactions to form distinct dimeric pairs. The other displays a novel dimeric structure built around a central four-membered Pb2Se2 ring. All new compounds have been characterised spectroscopically (31P, 1H, 13C NMR, IR, mass spectroscopy), by elemental analysis and five demonstrative X-ray structures are reported.