Poly (3-hexylthiophene) (P3HT) is one of the most efficient hole transport layers (HTLs) in perovskite solar cells (PSCs). However, surface and boundary defects in CsPbI3, and energy level mismatch between CsPbI3 and P3HT lead to a low power conversion efficiency (PCE) in P3HT-based CsPbI3 PSCs. Here, a synergistic strategy with anti-solvent (sec-pentyl alcohol, 2-PA) and passivators (LiX, X = F, Cl, Br, I) is developed to promote the photovoltaic performance of P3HT-based CsPbI3 PSCs. It is proved that the 2-PA washes away the residual DMF and DMAPbI3, and assists the secondary growth of CsPbI3 crystal. LiX not only can passivate iodine (I) vacancies, but also can reduce energy offset at CsPbI3/P3HT interface, accelerating hole extraction process. Finally, an impressive efficiency of 19.26% is obtained due to the synergistic effect of defects passivation and energy alignment, which is 34.4% higher than the 14.32% achieved in Control cell. These findings prove that synergistic strategy of defects passivation and energy alignment is an effective way for realizing high-efficiency in P3HT-based CsPbI3 PSCs.