Comprehensive SummaryPorous materials have been extensively developed and displayed special applications in diverse fields, however, it still remains a great challenge in developing new synthetic methods with features of energy‐saving and easy‐operating. In this study, we reported the construction of a series of novel ionic complexes based on discrete supramolecular triangle structure and polyoxometalate [Mo6O19]2–, using a quite efficient strategy. The obtained composites exhibit precise 3D network structures with ideal stability containing micropores, which were characterized by the 1H NMR, ESI‐MS, TEM, SEM, and single‐crystal X‐ray diffraction. These composites showed differential vapor adsorption behaviors for benzene, toluene, and cyclohexane. This work provides a novel approach for fabricating porous materials through electrostatic interactions and has great potential for gas separation.