Solvothermal reactions of Cd(OAc)2·2H2O with 3,3′-azodibenzoic acid (H2L) in N,N′-dimethylformamide (DMF) or DMF/MeOH at 100°C or 120°C gave rise to three cadmium(II) coordination polymers {[CdL(DMF)2]·0.5DMF}n (1), [CdL(DMF)(MeOH)]n (2) and {[Cd3L3(DMF)4]·0.5DMF}n (3). Complexes 1–3 were characterized by elemental analysis, IR, powder X-ray diffraction and single-crystal X-ray diffraction. In 1–3, dinuclear [Cd2L4(DMF)4] (1) or [Cd2L4(DMF)2(MeOH)2] (2) unit and trinuclear [Cd3L6(DMF)4] (3) unit acts as a four-connecting node to link its equivalent ones via sharing L ligands to form 2D layers, which are further connected through the C−H⋯π (1) or hydrogen-bonding interactions (2–3) to afford 3D networks with the 41263 topology. The network of 1 allows other one to be penetrated for the formation of twofold interpenetrating pcu net. The formation of 1–3 provided an interesting insight into solvent and temperature effects on the construction of coordination polymers under solvothermal conditions. In addition, the photoluminescent properties of 1–3 in solid state at ambient temperature were also investigated.