MXene has tremendous potential for enhancing thermal and tribological properties of fabric composites. Yet, its susceptibility to stacking and weak interfacial adhesion in organic matrix impedes practical application. Herein, MXene-h-BN hybrids were successfully achieved utilizing facile thiol-ene click reaction to introduce hexagonal boron nitride onto the surface of MXene to construct unique hierarchical structure. h-BN is grafted onto MXene through covalent bonding, effectively boosting interfacial adhesion and dispersion in the resin matrix. The layered MXene-h-BN possesses good lubrication behaviour, and h-BN can increase strength and thermal conductivity of the MXene support skeleton. The results demonstrate that the thermal conductivity, tensile and bonding strength of reinforced fabric composites are elevated by 43.28%, 34.25% and 43.75% compared with pure fabric composites, respectively. Additionally, the wear rate of reinforced fabric composites is significantly decreased by 63.44%. This paper will contribute a novel and prospective reinforcement design strategy for click reaction constructed nano-materials in tribology.