Neutral zinc, cadmium, mercury(II), and ethylmercury(II) complexes of a series of phosphinothiol ligands, PhnP(C6H3(SH-2)(R-3))(3-n) (n = 1, 2; R = H, SiMe3) have been synthesized and characterized by IR and NMR (H-1, C-13, and P-31) spectroscopy, FAB mass spectrometry, and X-ray structural analysis. The compounds [Zn{PhP(C6H4S-2)(2)}] (1) and [Cd{Ph2PC6H4S-2}(2)] (2) have been synthesized by electrochemical oxidation of anodic metal (zinc or cadmium) in an acetonitrile solution of the appropriate ligand. The presence of pyridine in the electrolytic cell affords the mixed complexes [Zn{PhP(C6H4S-2)(2)}(py)] (3) and [Cd{PhP(C6H4S-2)(2)}(py)] (4). [Hg{Ph2PC6H4S-2}(2)] (5) and [Hg{Ph2PC6H3(S-2)(SiMe3-3)}(2)] (6) were obtained by the addition of the appropriate ligand to a solution of mercury(II) acetate in methanol in the presence of triethylamine. [EtHg{Ph2PC6H4S-2}] (7),[EtHg{Ph2P(O)C6H3(S-2)(SiMe3-3)}] (8), [{EtHg}(2){PhP(C6H4S-2)(2)}] (9), and [{EtHg}(2){PhP(C6H3(S-2)(SiMe3-3))(2)}] (10) were obtained by reaction of ethyl mercury(II) chloride with the corresponding ligand in methanol. In addition, in the reactions of EtHgCl with Ph2C6H4SH-2 and with the potentially tridentate ligand PhP(C6H3(SH-2)(SiMe3-3))(2), cleavage of the Hg-C bond was observed with the formation of [Hg{Ph2PC6H4S-2}(2)] (5) and [Hg(EtHg)(2){PhP(O)(C6H3(S-2)(SiMe3-3))(2)}(2)] (11), respectively, and the corresponding hydrocarbon. The crystal structures of [Zn-3{PhP(C6H4S-2)(2)}(2){PhP(O)(C6H4S-2)(2)}] (1*), [Cd-2{Ph2PC6H4S-2}(3){Ph2P(O)C6H4S-2}] (2*), 3, 5, 6, [EtHg{Ph2P(O)C6H4S-2}] (7*), 8, 9, [{EtHg}(2){PhP(O)(C6H3(S-2)(SiMe3-3))(2)}] (10*), and 11 are discussed. The molecular structures of 1, 2, 4, 7, and 10 have also been studied by means of density functional theory (DFT) calculations.