In this study, we employed facile aminative cyclizations (Chichibabin pyridine reactions) of 1,1′-diacetylferrocene (AFC) with aryl aldehydes to prepare conjugated microporous polymers (CMPs) containing ferrocene moieties, for supercapacitor applications. The chemical structure of these AFC-CMPs frameworks was proved by using FTIR and solid 13C NMR spectroscopies. All these AFC-CMPs featured outstanding thermal stability with decomposition temperature (Td10) ranging from 309 to 337 °C and also these AFC-CMPs possess an amorphous structure with BET values in the range 72–341 m2 g−1. Among our tested systems, the BP-FC-CMP electrode achieved the highest specific capacitance of 608 F g−1 at a 0.5 A g−1 and the highest capacity retention of 97.47% after 2000 cycles and good CO2 ability uptake. This behavior arose from its high porosity facilitating redox reactions with faster kinetics. These novel metal-free CMPs have promise for application in secondary energy devices.