High-strength Cu–25Zn–5Al–3Fe–3Mn brass has broad applications as a wear-resistant copper alloy, while its tribological behavior at high temperatures has not yet been well investigated. In this paper, the tribological behavior of Cu–25Zn–5Al–3Fe–3Mn alloy was investigated at room temperature –500 °C coupled with AISI 316L and AISI 440C stainless steel. The effects of test temperatures and counterparts on its tribological properties were systemically discussed. The results indicate that the friction and wear behavior are largely dependent on the test temperatures and counterparts. And there exists a clear distinction in the friction and wear behavior when the alloy sliding against different counterparts at RT–500 °C. The tribological properties of the alloy depend on the counterparts at RT–200 °C due to that the main wear mechanism is abrasive wear for Cu/316L pairs and plastic deformation for Cu/440C pairs. When the test temperature exceeds 300 °C, the adhesive wear is main wear mechanism. The softening resistance and oxidation process is decisive for the high temperatures tribological behavior.