In this study, we used effective and one-pot Heck coupling reactions under moderate reaction conditions to construct two new hybrid porous polymers (named OVS-P-TPA and OVS-P-F HPPs) with high yield, based on silsesquioxane cage nanoparticles through the reaction of octavinylsilsesquioxane (OVS) with different brominated pyrene (P-Br₄), triphenylamine (TPA-Br₃), and fluorene (F-Br₂) as co-monomer units. The successful syntheses of both OVS-HPPs were tested using various instruments, such as X-ray photoelectron (XPS), solid-state ¹³C NMR, and Fourier transform infrared spectroscopy (FTIR) analyses. All spectroscopic data confirmed the successful incorporation and linkage of P, TPA, and F units into the POSS cage in order to form porous OVS-HPP materials. In addition, the thermogravimetric analysis (TGA) and N₂ adsorption analyses revealed the thermal stabilities of OVS-P-F HPP (T_d10 = 444 °C; char yield: 79 wt%), with a significant specific surface area of 375 m² g^–1 and a large pore volume of 0.69 cm³ g^–1. According to electrochemical three-electrode performance, the OVS-P-F HPP precursor displayed superior capacitances of 292 F g⁻¹ with a capacity retention of 99.8% compared to OVS-P-TPA HPP material. Interestingly, the OVS-P-TPA HPP showed a promising HER value of 701.9 µmol g⁻¹ h⁻¹, which is more than 12 times higher than that of OVS-P-F HPP (56.6 µmol g⁻¹ h⁻¹), based on photocatalytic experimental results.