The synthesis and characterization of 10-(o-alkoxyphenyl)phenoxarsines 2-ROC6H4As(C6H4)(2)O (R = H, Me, and Pr-i, As(C6H4)(2)O = phenoxarsine) and their platinum(II) and palladium(II) complexes cis-[PtCl2{2-(PrOC6H4As)-O-i(C6H4)(2)O-kappa As}(2)] (1), trans-[PdCl2{2-(PrOC6H4As)-O-i(C6H4)(2)O-kappa As}(2)} (2), cis-[PtCl2{2-HOC6H4As(C6H4)(2)O-kappa As}(2)] (3), cis-(PdCl2(2HOC(6)H(4)As(C6H4)(2)O-kappa As}(2)] (4), cis-[Ptl(2){2-MeOC6H4As(C6H4)(2)O-kappa As}(2)] (5), and trans-[PdCl2(2-MeOC6H4As(C6H4)(2)O-kappa As}(2)] (6) are reported. The chelate complex cis-[Pt{2-OC6H4As(C6H4)2O-kappa As, O}(2)] (7) is also described. The molecular structures of 14 and 7 were determined. The short As center dot center dot center dot O intramolecular interaction found in complexes 14 in the solid state was also verified by calculations at the B3LYP/LANL2DZ level for complex 2 and for 10-(o-isopropoxyphenyl)phenoxarsine in the gas phase, and this suggests that the interaction is a characteristic of the ligand rather than a packing effect. Calculations at the B3LYP/LANL2DZ and Oniom(B3LYP/LANL2DZ:uff) levels for complexes 14 showed that the solvent plays a crucial role in the crystallization (through geometry constraints) of the kinetically stable cis isomers.