Molybdenum dithiocarbamate (MoDTC) could effectively enhance the friction-reducing, anti-wear, and load-bearing capacity between mechanical friction pairs, but further improvement was essential. In this study, the layered double hydroxides (LDHs) with various chemical compositions were synthesized and subsequently employed alongside MoDTC to investigate the tribological properties of poly α olefin 8 (PAO8). It was found that the variation of composition had significant impacts on the friction performance of PAO8. The addition of Ni/Al LDHs with proper concentration, whether used alone or in conjunction with MoDTC, could greatly boost the tribological properties of PAO8. Notably, the synergistic effect between Ni/Al LDHs and MoDTC accelerated the forming rate of tribofilm composed of various metal oxides and sulfates, ultimately enhancing load-bearing and tribological properties.