Under high load and sliding velocity conditions, the thickness of lubricant films decreases to a nano-scale, which is referred to as the boundary lubrication. In the boundary lubrication regime, the molecular structure of boundary lubricant plays a key role in lubrication performance. In this study, the friction forces of supramolecular films of selected model boundary lubricants were measured by smploying a friction force microscopy (FFM) in order to provide a better understanding on the relationship between the molecular structure and the tribological behavior. In addition, the macroscopic friction force data of the model boundary lubricants were obtained by using a tribometer, compared with the FFM results and discussed in terms of the structure of model boundary lubricant.