Addition of the potassium dichalcogenidodiphenylphosphinate salts, KE 2 PPh 2 (E=S, Se), to either the THF solvate of vanadium (III) chloride or unsolvated chromium(III) chloride results in rapid ligand substitution and the formation of a series of closelyrelated trivalent, neutral mononuclear complexes, M(E 2 PPh 2 ) 3 (M=V, Cr; E=S, Se), isolated in modest to good yield. The metal dichalcogenidophosphinate complexes reported herein were characterized by IR, UV-vis, and 1 H NMR spectroscopies, and their solid-state molecular structures were determined by single-crystal X-ray crystallography. Importantly, the comparative analysis includes the structural and spectroscopic studies of two rare V(III) dithio-and diseleno-phosphinate VE 6 cores, as well as, two previously known CrE 6 analogues. In the solid-state the title complexes exhibit trigonal distortion from octahedral with torsion angles ranging from 43(2) to 50.3(6)°and structural parameters consistent with ligation of progressively 'softer' chalcogen-donors.