The incorporation of [Mn(2,2'-bipy)(2)](2+) with thioarsenate resulted in the formation of two novel compounds, [Mn3-(2,2'-bipy)(3)((AsS4)-S-V)(2)](n), nH(2)O (1) and Mn-2(2,2'-bipy) (As2S5)-S-III (2), in which the main-group chalcogenide framework is incorporated with a [tm(2,2'-bipy)(m)](n+) complex. Meanwhile, the tetrathioarsenate(V) anion acts as a new mu(3-)1 kappa S: 1,2 kappa S':2,3 kappa S'': 3 kappa S''' ligand in 1, in which all four S atoms of the [(AsS4)-S-V](3-) anion are coordinating to metal. As a result, the two compounds exhibit semiconducting properties (E-g) 2.18 eV (1) and 1.83 eV (2)) and strong blue photoluminescence, with the emission maximum occurring at about 440 nm. Magnetic measurements show that both compounds have AF ordered states with Neel temperatures of 19 and 24 K for 1 and 2, respectively.