Quests for advanced functionalities in metal-organic frameworks (MOFs) inevitably encounter increasing complexity in their tailored framework architectures, accompanied by heightened challenges with their geometric design. In this paper, we demonstrate the feasibility of rationally exploiting topological prediction as a blueprint for predesigned MOFs. A new triangular frusta secondary building unit (SBU), {Zn-4(tz)(3)}, was bridged by three TDC2- fragments to initially form a trigonal prismatic node, {Zn-8(tz)(6)(TDC)(3)} (Htz = 1H-1,2,3-triazole and H2TDC = 2,5-thiophenedicarboxylic acid). Furthermore, the trigonal prism unit can be considered as a double SBU derived from triply bound triangular frusta. By considering theoretical derived nets for linking this trigonal-prismatic node with ditopic, tritopic, and tetratopic linkers, we have synthesized and characterized a new family of MOFs that adopt the decorated Ion, jea, and xai nets, respectively. Pore sizes have also been successively increased within TPMOF-n family, which facilitates heterogeneous biomimetic catalysis with Fe-porphyrin-based TPMOF-7 as a catalyst.