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Quasi-2D Ruddlesden-Popper perovskites exhibit excellent photostability/environmental stability. However, the main drawback is their relatively low photovoltaic properties compared with three-dimensional perovskites. Herein, we demonstrated that chlorine-based additives via adjusting the proportion of PbI2 and PbCl2 in the precursor (BA)2(MA)3Pb4I13 (n = 4) solutions show an optimized device performance of over 15%, and the devices exhibit much improved humidity stability. Upon PbCl2 addition, the quasi-2D perovskites have larger