Abstractπ‐Conjugated polyelectrolytes (CPEs) have been studied as interlayers on top of a separate hole transport layer (HTL) to improve the wetting, interfacial defect passivation, and crystal growth of perovskites. However, very few CPE‐based HTLs have been reported without rational molecular design as ideal HTLs for perovskite solar cells (PeSCs). In this study, the authors synthesize a triphenylamine‐based anionic CPE (TPAFS‐TMA) as an HTL for p‐i‐n‐type PeSCs. TPAFS‐TMA has appropriate frontier molecular orbital (FMO) levels similar to those of the commonly used poly(bis(4‐phenyl)‐2,4,6‐trimethylphenylamine) (PTAA) HTL. The ionic and semiconducting TPAFS‐TMA shows high compatibility, high transmittance, appropriate FMO energy levels for hole extraction and electron blocking, as well as defect passivating properties, which are confirmed using various optical and electrical analyses. Thus, the PeSC with the TPAFS‐TMA HTL exhibits the best power conversion efficiency (PCE) of 20.86%, which is better than that of the PTAA‐based device (PCE of 19.97%). In addition, it exhibits negligible device‐to‐device variations in its photovoltaic performance, contrary to the device with PTAA. Finally, a large‐area PeSC (1 cm2) and mini‐module (3 cm2), showing PCEs of 19.46% and 18.41%, respectively, are successfully fabricated. The newly synthesized TPAFS‐TMA may suggest its great potential as an HTL for large‐area PeSCs.