In order to circumvent the contradiction between processability and electrochemical performances, we report a recombination strategy in both unit and segment scales for processable ambipolar electroactive materials starting from parental moieties: classic ambipolar polymer (PEBE) and its soluble analogue (PPBP). On the basis of this strategy, two recombined polymers (PEB-P and PEBE-PBP) are successfully prepared via direct (hetero)arylation copolymerization. Through systematical characterization of properties, both PEB-P and PEBE-PBP not only possess the solubility fostered by PPBP but also exhibit identical electrochemical and optical properties to PEBE, demonstrating the reliability of this recombination strategy. Moreover, film electrodes of these recombined polymers exhibit desirable pseudocapacitance, acceptable stability, and superior processability to PEBE, making them promising candidates for Type III supercapacitors and other multifunctional energy storage devices.