In our work, we have been synthesized two-hybrid porous organic-inorganic microporous polymers (POIPs) through a simple and friendly Heck coupling reaction at a moderate temperature of cubic octavinylsilsesquioxane (OVS) with brominated fluorene (F–Br₂) and anthraquinone (A-Br₂); respectively, to afford POSS-F-POIP and POSS-A-POIP. FTIR, solid-state ¹³C, and ²⁹Si NMR spectroscopy analyses were carried out to confirm the chemical structures of these POIP materials and the presence of POSS units within their framework. TGA measurements revealed that POSS-A-POIP possesses high thermal stability (T_d10: 600 ^◦C, and char yield: 83 wt%) due to the presence of rigid anthraquinone and POSS units. Furthermore, POSS-A-POIP features pseudocapacitor with high symmetry and high specific capacitance of 152.5 F g^-1 at 0.5 A g^-1 when compared with the POSS-FPOIP (36.2 F g^-1 at 0.5 A g^-1). The excellent energy storage performance of POSS-A-POIP could be attributed to the Faradaic reaction of anthraquinone and the π-conjugated system.