Recent years have witnessed the acceleration of research on tribochemical reactions in the tribology area. Together with new experimental findings, atomic modeling has increasingly contributed to the understanding of mechanistic insights and interpretation of tribochemical reactions and related frictional outcomes. Apart from showing agreement with experiments, efforts have been paid to develop simulation codes and models to bring simulations closer to practical tribotests with a reasonable computational expense. By simulations and modeling, tribochemical reactions and physical/chemical interactions between lubricants, surface-lubricant, contacting interfaces, and surface/lubricant-environmental agents have been investigated. This work provides an up-to-date review of studies on physical/chemical interactions and tribochemical reactions in tribosystems using atomic computational simulations such as reactive force fields, quantum mechanics, and quantum mechanics/molecular dynamics. On the basis of the current development, we outline future prospects for the simulation and modeling section in the field of tribochemistry.