A series of hybrid luminescent porous polymers (HLPPs) are synthesized through Friedel–Crafts reactions by tuning the molar ratio of triphenylamine (TPA) to octavinylsilsesquioxane (OVS). The synthesized HLPPs exhibit high Brunauer–Emmett–Teller surface areas up to 841±10 m² g⁻¹, high thermal stability with decomposition temperatures (T_d at 5 wt %) up to 440 °C in air, and strong blue–violet luminescence at approximately 450 nm. The porosities and luminescent properties of the HLPPs, including emission wavelength, intensity, fluorescence quantum yield, and monochromaticity, can be tuned easily by modulating the molar ratio of TPA to OVS. In addition, the polymers may serve as excellent fluorescent probes for multianalyte detection, with high fluorescence quenching coefficients (K_SV) of 8900 and 4400 m⁻¹ for Fe³⁺ and Cu²⁺, respectively.