PANI:PSS modified with a nonionic surfactant (Triton X–100) was successfully utilized as a hole transport material for perovskite solar cells. Perovskite solar cells using PANI:PSS with the optimal Triton X–100 concentration exhibited a maximum power conversion efficiency of 11.67%. Triton X–100 played a bifunctional role to enhance the hole extraction capability of PANI:PSS.