A complete understanding of the mechanism of boundary lubrication is a goal that scientists have been striving to achieve over the past century. Although this complicated process has been far from fully revealed, a general picture and its influencing factors have been elucidated, not only at the macroscopic scale but also at the nanoscale, which is sufficiently clear to provide effective instructions for a lubrication design in engineering and even to efficiently control the boundary lubrication properties. Herein, we provide a review on the main advances, especially the breakthroughs in uncovering the mysterious but useful process of boundary lubrication by adsorption film. Despite the existence of an enormous amount of knowledge, albeit unsystematic, acquired in this area, in the present review, an effort was made to clarify the mainline of leading perspectives and methodologies in revealing the fundamental problems inherent to boundary lubrication. The main content of this review includes the formation of boundary film, the effects of boundary film on the adhesion and friction of rough surfaces, the behavior of adsorption film in boundary lubrication, boundary lubrication at the nanoscale, and the active control of boundary lubrication, generally sequenced based on the real history of our understanding of this process over the past century, incorporated by related modern concepts and prospects.