Two cadmium coordination polymers, WSU-30 and WSU-31, were synthesized through solvothermal methods by using the low-symmetry TPE-based linker m-H4ETTC. The m-H4ETTC linker and both coordination polymers were fully characterized by using single-crystal X-ray diffraction, infrared spectroscopy, and photoluminescent emission spectroscopy. Structural analysis of WSU-30 and WSU-31 showed that each compound contains previously unknown tetranuclear cadmium(II) secondary building units. The topological analysis revealed that the 4,8-connected net of WSU-30 contains the underlying topology, alb-4,8-P21/c-1, while the mixed linker WSU-31 possesses a 3,10-connected net known as 3,10T31 topology. If the m-ETTC linker is considered as two 3-connected nodes, WSU-30 possesses a very rare 3,3,8-connected 3,3,8T25 topology, and WSU-31 possesses a previously unknown 3,12-connected net, named 3,12T61.