Phenolic resin (PF) coatings were formulated and deposited onto Al alloy surfaces, and their tribo-performance was evaluated. It is demonstrated that even when being lubricated with poly(alpha olefin) 4 (PAO 4) base oil, the PF-based coatings reinforced with titanium dioxide (TiO₂) or/and nickel (Ni) exhibit excellent tribo-performance under harsh boundary lubrication conditions. Interestingly, synergetic antiwear roles of TiO₂ and Ni were identified. In comparison to the conventional PF coating filled with molybdenum disulfide (MoS₂), friction and wear of the hybrid coating containing TiO₂ and Ni are reduced by up to 80.7% and 83.2%, respectively. Furthermore, the hybrid coating lubricated with PAO 4 base oil exhibit a much lower friction and wear than the uncoated Al alloy lubricated with zinc dialkyldithiophosphat (ZDDP)-additivated oil. Our work provides direct evidence that the addition of TiO₂ or Ni leads to the growth of tribofilms of distinctly different nanostructures. It is interesting that the addition of a TiO₂/Ni combination gives rise to the formation of a double-layered tribofilm, i.e., a TiO₂/NiO bottom layer and a carbon-based top layer. This work offers an avenue for minimizing dependency on hazardous lubrication additives.