Owing to good self-lubricating performance, tin bronze is widely used in industrial fields. As tin bronze parts manufactured by powder metallurgy, their tribological performances are influenced by raw powder. In this work, four types of self-lubricating copper alloy composites (CuSn10 (D), CuSn10, CuSn10Pb10 (D) and CuSn10Pb10) were prepared by sintering completely alloyed powder and diffusion alloyed copper tin powder. The morphology, element distribution and microstructure of raw powder and their sintered Cu alloy composites were observed. The tribological properties of Cu alloys were investigated by block-ring friction test under different working conditions and their worn surface and wear debris were analyzed. The results show that the diffusion alloyed powder has an irregular dendritic morphology and its sintered Cu alloy is more likely to produce twin structure which enhances the hardness and the bearing capacity of the material. Compared with completely alloyed powder sintered CuSn10 sample, the wear rate of CuSn10 (D) sintered from diffusion alloyed powder was reduced by 83.96%, 74.39%, and 67.63% under three typical working conditions. Under dry friction conditions, the wear rate of CuSn10 (D) is reduced by 63.64% than CuSn10, and CuSn10Pb10 (D) is 25% lower than CuSn10Pb10. The investigation on the wear tracks and wear debris of Cu alloy composites showed that the diffusion alloyed powder sintered samples are inclined to form a more consecutive and integral third-body layer on wear tracks and which contributes to the better wear resistance.