In braking materials field, MAX phase has been introduced into Cu-based composite materials to address issues such as inadequate wetting between ceramic particles and the metal matrix. This study focuses on preparing Ti2AlN-ZrO2-B4C reinforced Cu-based materials via the powder metallurgy method, and investigates the effects and mechanisms of different Ti2AlN/ZrO2 ratios on the mechanical, thermal, and tribological properties of these materials. The addition of an appropriate amount of Ti2AlN (3 wt%) can enhance the densification and mechanical properties of Cu-based materials, as the diffusion of Al atoms promotes the sintering process. Similarly, the diffusion of Al also improves the thermal conductivity at grain boundaries, resulting in samples with higher Ti2AlN content exhibiting superior thermal diffusivity. When the Ti2AlN content reached 7 wt%, the material exhibited optimal hardness (43.35 ± 1.05 HBW), moderate shear strength (19.84 ± 1.86 MPa), as well as excellent high initial braking speed friction coefficient and stability. The reinforcement primarily arises from the diffusion bonding between Ti2AlN and Cu, leading to the formation of Cu-Ti compounds at the interface, which facilitates Ti2AlN in providing frictional force during the friction process and promotes the formation of a friction film due to the “pinning effect”. Additionally, the layered structure of Ti2AlN and the subsequent formation of amorphous Al2O3 after oxidation contributed to the enhancement of friction stability.