In this study, we synthesized three hybrid microporous polymers through Heck couplings of octavinylsilsesquioxane (OVS) with 2,5-bis(4-bromophenyl)-1,3,4-oxadiazole (OXD-Br₂), tetrabromothiophene (Th-Br₄), and 2,5-bis(4-bromophenyl)-3,4-diphenylthiophene (TPTh-Br₂), obtaining the porous organic–inorganic polymers (POIPs) POSS-OXD, POSS-Th, and POSS-TPTh, respectively. Fourier transform infrared spectroscopy and solid state ¹³C and ²⁹Si NMR spectroscopy confirmed their chemical structures. Thermogravimetric analysis revealed that, among these three systems, the POSS-Th POIP possessed the highest thermal stability (T₅: 586 °C; T₁₀: 785 °C; char yield: 90 wt%), presumably because of a strongly crosslinked network formed between its OVS and Th moieties. Furthermore, the specific capacity of the POSS-TPTh POIP (354 F g⁻¹) at 0.5 A g⁻¹ was higher than those of the POSS-Th (213 F g⁻¹) and POSS-OXD (119 F g⁻¹) POIPs. We attribute the superior electrochemical properties of the POSS-TPTh POIP to its high surface area and the presence of electron-rich phenyl groups within its structure.