To develop superior piston pump friction pair materials in harsh working conditions, the tribological properties of two novel copper-based composites, C93800 copper alloy casting material and 10–10 powder metallurgy copper steel bimetallic plate, as tribo-pairs of a piston pump were evaluated on an end-face tribometer. Their tribological behavior and extreme pressure x velocity (PV) values (PV value is an important indicator that reflects the performance of sliding bearings and is the product of the unit bearing load and the restricted linear speed) were analyzed. The results show that both the two copper-based composites had excellent antifriction and antiwear performances. The 10–10 powder metallurgy copper steel bimetallic plate shows better wear resistance and superior tribological performance due to its higher hardness. However, its extreme PV value is lower than the C93800 copper alloy casting material, since the latter can play a buffer during the loading process. In addition, the extreme PV value of the C93800 copper alloy casting material amounted to 40 MPa·m/s, showing promising potential for industrial application.