Seven new CPs, {[Zn(thim(2))(o-BDC)]center dot(H2O)(2)}(n) (1), [Co(thim(2))(m-BDC)](n) (2), {[M(thim(2))(HBTC)]center dot(H2O)}(n) [M = Co(3) and Zn(4)], {[M(thim(2))(OBA)]center dot(H2O)(2)}(n) [M = Co(5) and Zn(6)], [Mn-2(thim(2))(2)(m-BDC)(2)(H2O)](n) (7) [o-H2BDC = phthalic acid, m-H2BDC = isophthalic acid, H3BTC = trimesic acid, H(2)OBA = 4,4'oxybis(benzoic acid)], have been prepared by hydro/solvothermal reaction of different metal salts with 2,5-bis(imidazol-1-yl) thiophene (thim(2)) in the presence of various multicarboxylic acids. CP 1 exhibits a 2D herringbone pleated network structure. CP 2 reveals a 2D + 2D = 3D polycatenated framework composed of a 2D parallel pleated network. CPs 3 and 4 show isostructural 2D herringbone pleated networks. CPs 5 and 6 are also isostructural and form a 2D layer structure arranged in a ...ABAB... pattern in the crystal lattice. CP 7 forms a 3D framework consisting of 1D [Mn-2(m-BDC)(2)(H2O)](n) chains linked by thim(2). The structures of all five type of CPs indicate that different multicarboxylate coligands play an important role in structural variation. The thermal stabilities of all the CPs (1-7) were monitored by TGA. Furthermore, solid state photoluminescence was investigated for 1, 4 and 6 at room temperature.