Although a number of chalcogenostannates have been obtained by using [M(amine)m]n+ as the structure director, these materials with chiral metal complex ions are usually achiral because they are a racemic mix of chiral complex cations. A chiral selenidostannate, [Mn(tepa).Sn3Se7]n (1; tepa = tetraethylenepentamine), containing incorporated [Mn(tepa)]2+ units, is reported herein. The unique structure is just like a grapevine appended with chiral grapes. In the same reaction, a centrosymmetric compound, [Mn(tepa)]2(mu2-Sn2Se6) (2), in which the Sn2Se64- anion acts as a bridge coordinating to [Mn(tepa)]2+ cations, has also been obtained. This is a reaction-time-related process in which compound 2 transformed gradually to 1 after prolonging the reaction time. This phenomenon demonstrates a transformation from achiral to chiral and dimeric to polymeric selenidostannate.