Tri(2-thiophenyl)phosphine (P(C6H4-2-SH)3,PS3) was designed at 1989. Recently chemists use this ligand for enzyme models because it provides rich sulfur environment. Some chemists use PS3 to synthesize novel metal complexes. This thesis deals with the synthesis and structural discussion of germanium and tin complexes bearing PS3 ligands. Reactions with different metal source all yield novel structures. Reaction of GeCl4 with PS3 gives supramolecular structures with continuous £k-£k interaction. Similar reaction with GeCl3Me gives crystals in optically active form in stead of the usual optically inactive racemic form. Reaction with SnCl4 gives six-coordinate dimmeric tin complex (Sn(OMe)(PS3))2 with bridging methoxyl group and thiolate group (from PS3). Reactions using SnCl3Et or SnCl3Bu as metal sources followed by sublimation (140oC , 10-2torr) give reductive elimination products with alkyl groups transferred onto sulfur atom. These two structures are similar in morphology but different in skeletal arrangement.