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In this paper, a series of monomers (M1-M7) were facilely synthesized by Passerini reaction and the subsequent in-situ polymerization led to the formation of the conductive poly(indole/thiophene)s (P1-P7). Among P1-P7, it was found through the comparison that P7-P with a higher conjugated system exhibits an outstanding specific capacitance of 1170 F g−1 (scan rate 1 mV s−1), power density of 2614.4 W kg−1 and energy density of 56.5 Wh kg−1 (5 A g−1). The capacitance performance of P7-P complexed with Fe3+ system is further increased by 130 F g−1 because of the redox reaction of Fe3+. Using the chronoamperometry, the minimum detection limit of polymer P7-P for Fe3+ is 3 × 10−5 M. In summary, the facile synthesis of the conductive poly(indole/thiophene) polymers, their excellent energy storage and Fe3+ detection performance, open an opportunity for functional polymers in the energy storage and sensor applications.