With assistance of reactive and coordinative hydrazine, transition-metal telluromercurates [Mn(trien)(N2H4)(2)](2)[Hg2Te4](2) (A), [Zn(trien)(N2H4)(2)]Hg2Te4 (B), [Mn(tepa)(N2H4)](2)Hg4Te12 (C), [TM(trien)(Hg2Te4)] (TM = Mn (D), Zn (E)), and [Zn(atep)](2)Hg3Te12 (atep = 4-(2aminoethyl)triethylenetetramine) (F) were solvothermally prepared in triethylenetetramine (trien) or tetraethylenepentamine (tepa) solvents using elemental Te as precursor in lower temperature range. Compounds A and B consist of mixed coordination cations [TM(trien)(N2H4)(2)](2+) (TM = Mn, Zn) and one-dimensional polyanion [Hg2Te4](2-) with the five-membered Hg2Te3 rings being coplanar. Compound C is composed of two [Mn(tepa)(N2H4)](2+) cations and a [Hg4Te12](4-) cluster with a centrosymmetric structure. Compounds D and E consist of coordination polymer [TM(trien) (Hg2Te4)] containing novel doubled [Hg2Te4] chain with tetrahedrally coordinated Hg(II) centers, which is quite different from the common single chain with the same composition of [Hg2Te4],. D and E are the first examples of telluromercurates incorporated with TM complex units via TM Te bonds. Compound F contains fivefold coordinated [Zn(atep)](2+) cations and zigzag [Hg5Te124-],, polymeric anion. The [Hg5Te124-] anion is a new species of the binary telluromercurates. It is built from [Hg4Te6] and [HgTe2(Te-4)] subunits via interconnectivity, which generates Hg3Te3 and Hg4Te4 rings in the structure. Compounds A F are potential semiconductors with narrow band gaps in the range of 0.961.09 eV. Photocatalytic investigation of Mn(II) complexes show that they are photocatalytically active in the degradation of CV under visible-light irradiation with the highest catalytic effective of cluster compound C.