In this study, four novel silafluorene (SiF) and benzotriazole (Btz) bearing conjugated polymers are synthesized. In the context of electrochemical and optical studies, these polymers are promising materials both for electrochromic device (ECD) and polymer solar cell (PSC) applications. All of the polymers are ambipolar (both p‐ and n‐dopable) and multichromic. Electrochemistry experiments indicate that incorporation of selenophene instead of thiophene unit increases the HOMO energy level of the polymers. Power conversion efficiency of the PSCs reached 1.75% for PTBTSiF, 1.55% for PSBSSiF, 2.57% for PBTBTSiF, and 1.82% for PBSBSSiF. The hole mobilities of the polymers are estimated through space charge limited current (SCLC) model. PBTBTSiF has the highest hole mobility as 2.44 × 10−3 cm2 V s−1. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015, 53, 1541–1547