Stability is one of the major issues for hybrid organic− inorganic halide perovskites. In the organic aspect, increased hydrophobicity can be beneficial to the enhanced stability. Different from the previous R group hydrophobic modification in an organic R-NH 3 + cation, herein, NH 3 + modification using epoxide is reported to improve the stability of hybrid halide perovskites. We integrate the chiral propylene oxide (PO) into HDAPbI 4 (HDA = 1,6-hexamethylenediamine) through the grafting of PO onto HDA. The −NH 3 + hydrophobic modification is very favorable for stability improvement. As a result, the resultant (R/S-PO-HDA)PbI 4 thin film is stable in water for more than 1 h, whereas the untreated HDAPbI 4 thin film decomposes immediately. Moreover, (R/S-PO-HDA)PbI 4 could keep the photoelectricity of HDAPbI 4 and the chirality of PO. This work could inspire further study on the perovskite-based epoxide polymer.