The exploration of unleaded free-cutting Cu40Zn brass with excellent mechanical and tribological properties has always drawn the attention of researchers. Due to its attractive properties combining metals and ceramics, Ti3AlC2 was added to Cu40Zn brass using high-energy milling and hot-pressing sintering. The effects of Ti3AlC2 on the microstructure, mechanical and tribological properties of Cu40Zn-Ti3AlC2 composites were studied. The results showed that Ti3AlC2 could suppress the formation of ZnO by adsorbing oxygen impurity and promote the formation of the β phase by releasing the β-forming element Al to the substrate. The hardness and wear resistance of Cu40Zn-Ti3AlC2 composites increased with increasing Ti3AlC2 content from 0 to 5 wt.%. The proper Ti3AlC2 additive was beneficial to both the strength and plasticity of the composites. The underlying mechanisms were discussed.