Two-dimensional (2D) Ruddlesden-Popper (RP) CsPbI3 exhibits enhanced phase stability compared with 3D CsPbI3. However, the issue of the uncontrollable crystallization process limits its photovoltaic performance. Here, the influence of a binary mixed solvent on the film quality and photovoltaic properties of (PEA)2Cs4Pb5I16 (n = 5) is studied in detail. It is demonstrated that the crystallization rate and crystal growth can be controlled by adjusting the amount of dimethyl sulfoxide (DMSO). Optimizing the solvent composition with adding 10% DMSO in pure dimethyl formamide (DMF) leads to perfect coverage, larger flaky 2D grains, reduced grain boundaries, and a better vertical orientation to the substrate due to the formation of a more stable intermediate phase. This can form good interface contact, which is beneficial to charge transport/extraction between TiO2 (electron transport layer, ETL) and perovskite, finally resulting in improved device performance. The enhancement of the power conversion efficiency of the optimized device based on DMF/DMSO (9:1) is 3.57% compared with the reference device based on pure DMF. This work illustrates the role of crystallization kinetics in the RP CsPbI3 film and offers a simple and effective method for high-performance 2D CsPbI3 solar cells.