Lubricating oils play an important role in friction-reducing and anti-wear, as well as enhancing mechanical efficiency. To improve the oxidation stability and service life of lubricating oils, the composition and structure of antioxidants should be strategically designed, and these parameters have significantly affected the performance of antioxidants in lubricating oils. Antioxidants are classified into two types based on the substrates they act on: peroxide decomposers and radical scavengers. In this review, the effects of peroxide decomposers (including sulfur compounds, phosphorus compounds, sulfur–phosphorus compounds, and sulfur–nitrogen compounds) and radical scavengers, such as hindered phenols and aromatic amines, have been discussed as additives in the antioxidant properties of lubricating oils. The results indicate that peroxide decomposers have excellent performances in lubricating oils, but high pollution of S and P is not conducive to their widespread use. On the contrary, radical scavengers also have superior antioxidant properties and no pollution, possessing the potential to replace traditional antioxidants. In addition, molecular structures with (multiple) synergistic antioxidant properties have been extensively designed and reported. This review serves as a reference for researchers to design and develop high-end new antioxidants.