The increasing demand for low-viscosity engine oil has underscored the role of zinc dialkyldithiophosphates (ZDDP) as a conventional anti-wear and antioxidant additive. It is essential to investigate the influence of modern additives such as cyclopropanecarboxylic acid (CPCa) and Ni nanoparticles on the tribological performance of ZDDP for practical commercial oil application. According to the experimental results, Ni nanoparticles formed a protective film that exhibited a synergistic effect with ZDDP. A significantly higher concentration of sulphur in the tribofilm was detected compared to ZDDP by itself, which was responsible for a 27.6% lower wear loss. Meanwhile, a competitive effect between CPCa and ZDDP resulted in a dramatic increase in friction and unstable anti-wear performance. This was demonstrated by a localized formation of the ZDDP tribofilm on the wear surfaces after the friction test. These results have highlighted the synergistic and competitive effects of emerging additives (CPCa and Ni nanoparticles) in the ZDDP tribofilm formation between the sliding steel contacts. This further suggests a new approach to increase the efficiency of ZDDP’s tribological performance at cold start-up processes.