The copper content in copper sulfide significantly influences the material properties, potentially affecting interfacial non‐radiative recombination in perovskite solar cells. Here, a simple ball‐milling strategy is used to obtain Cu‐poor (cupric sulfide, CuS) and Cu‐rich (cuprous sulfide, Cu2S) nanoparticles (in which CuS and Cu2S are the dominant phases respectively, containing a mixture of CuO/Cu(OH)2 species) from commercial cupric‐ and cuprous‐sulfide powders respectively. The resulting Cu‐poor nanoparticles exhibit a well‐crystallized hexagonal structure, suppressing the formation of harmful CuO/Cu(OH)2 byproducts. Additionally, the Cu‐poor nanoparticles uniformly cover the perovskite, effectively addressing residual PbI2 at grain boundaries and constructing a hole‐transport channel at the interface between perovskite and spiro‐OMeTAD [2,2′,7,7′‐tetrakis (N, N‐di‐p‐methoxyphenylamine)‐9,9′‐spirobifluorene]. In contrast, the Cu‐rich nanoparticles exhibit a non‐crystalline structure with excessive CuO/Cu(OH)2 byproducts. Their aggregation and non‐uniform morphology on the perovskite surface likely result from the charge‐controlled interactions from the big bond polarity in cupric sulfide. Moreover, the presence of excessive CuO/Cu(OH)2 byproducts increases hydrophilic sites, weakening interfacial defect passivation and compromising device performance. Consequently, perovskite solar cells using copper‐rich CuS interface passivation layers achieved a champion power conversion efficiency (PCE) of over 25% and maintained ≈87% of the initial PCE after 2,300 h of storage in air, outperforming copper‐rich Cu2S‐based devices.