While dual‐acceptor‐type conjugated polymers have witnessed a great success in organic field‐effect transistors (OFETs), their potential multifunctionality in other optoelectronic devices has been overlooked. Herein, we designed, synthesized, and characterised three conjugated polymers (DPPF‐BDD, DPPT‐BDD and DPPSe‐BDD) comprising furan/thiophene/selenophene flanked diketopyrrolopyrrole (DPP) and dioxo‐benzodithiophene (BDD) as repeating units. Modulating the chalcogen on DPP flank showed an impact on dual‐acceptor polymers optoelectronic properties. Subsequently, we investigated the potential of these polymers in both OFETs and perovskite solar cells (PSCs) either as semiconductors or as passivation materials, respectively. Interestingly, DPPF‐BDD, DPPT‐BDD, and DPPSe‐BDD showed ambipolar behaviour in vacuum with hole (μh) and electron (μe) mobilities of 0.026/0.022, 0.022/0.012 and 0.007/0.005 cm2 V‐1s‐1, respectively. Upon doping tetrabutylammonium iodide into DPPF‐BDD, DPPT‐BDD and DPPSe‐BDD polymers, the respective OFETs showed relatively higher μh and μe (0.038/0.050; 0.028/0.025; 0.005/0.015 cm2V‐1s‐1) than the undoped polymer OFETs. Furthermore, DPPF‐BDD‐, DPPT‐BDD‐, and DPPSe‐BDD‐incorporated (in the antisolvent treatment and PCBM ETL) PSCs displayed maximum PCE of 23.48%, 22.85% and 23.35%, respectively, surpassing the control device (22.83%), which was benefited from the perovskite surface passivation and the charge extraction improvement. Overall, we present a new class of multifunctional DPP‐based dual‐acceptor‐type polymers that are highly compatible with OFETs and high‐performance PSCs.This article is protected by copyright. All rights reserved.