In this study, we successfully used the Suzuki-Miyaura reaction to prepare three novel conjugated microporous polymers (CMPs) that include tetraphenylethene (TPE): TPE-Ph-Th, TPE-Ph-Tha, and TPE-Ph-BSu. Using methods like FTIR and solid-state NMR, we examined the chemical composition and functional groups in the TPE-Ph CMPs. The TPE-Ph-BSu CMP's thermal characteristics were also examined, and they showed remarkable features with a decomposition temperature (T_d10) of 535 °C and a char yield of 73 wt%. We also looked at TPE-Ph-Th CMP, which had a pore size of 2.0 nm and a surface area (S_BET) of 67 m² g⁻¹. We carried out photoluminescence (PL) and electrochemical investigations to evaluate the potential of TPE-Ph CMPs for supercapacitor applications and their capability to detect p-nitrophenol (PNP). According to our electrochemical investigation, the TPE-Ph-Tha and TPE-Ph-BSu CMPs both exhibited exceptional capacitance, reaching 51 and 52 F g⁻¹ at a current density of 0.5 A g⁻¹, respectively. Furthermore, even after 5000 cycles, these CMPs still retained 80% of their capacitance, demonstrating their remarkable capacitance retention. In conclusion, synthetic TPE-Ph CMPs have several benefits, including outstanding electrochemical performance and thermal stability. Additionally, they successfully detect PNP using fluorescence-based sensing without interference, making them adaptable materials suited for a variety of applications, including the detection of pollutants (as PNP has shown) and the usage of supercapacitors.