Two new one-dimensional (1D) vanadium(III) chalcogenidostannates, [H(2)tepa](0.5n) [V-III(tepa)(mu-Sn(2)Q(6))](n) [Q= S (1), Se (2); tepa = tetraethylenepentamine], were achieved by solvothermal methods, which offer the first examples of organic hybrid polymeric chalcogenidostannates incorporating [V(tepa)](3+) complexes as bridging groups. Both 1 and 2 feature the 1D sinusoidal chains of [V-III(tepa)(mu-Sn(2)Q(6))](n) containing two types of novel bridging modes of the [mu-Sn(2)Q(6)](4-) anion. Their magnetic, photocurrent response, and optical properties are also studied.