Ionic liquids (ILs) are fascinating materials with unique combination of solid and liquid properties. Due to high thermal stability and promising tribological properties, there have been increasing research interests in applying ILs as boundary lubricants. In this review, the authors will discuss the recent progress on this topic with the emphasis on the relationship between the molecular arrangement of ILs confined to a solid and the tribological properties. First, the fundamentals on boundary lubrication and the state-ofthe-art lubricants will be reviewed briefly. Second, the progress on the molecular structure of ILs confined to a solid surface will be discussed. Afterward, the experimental and computational efforts on the ILs as boundary lubricants will be discussed in details with emphasis on the effect of IL structure, solid substrates, and IL-soild interaction. Finally, the future research directions will be discussed.