Tribofilm configuration under the boundary lubrication region is an essential concern to gain insight into the tribological enhancement of the two-dimensional (2D) nano materials toward base oils. In this work, several alkyl carboxylic acids modified 2D triazine-based covalent organic frameworks (ATC) nano platelets were fabricated and served as lubrication additives. When carbon atoms add up to 16, the best lubricating performance is exhibited at an additive concentration of 0.05 wt % and the friction coefficient and wear volume are, respectively, reduced by 56.0% and 89.6% as compared to those of pure PAO 10 base oil. The analysis of the focused ion beam-transmission electron microscope (FIB-TEM) on the worn surface reveals that an alternately multilayer tribofilm consisting of 2D platelet additives and oxides and/or metallic soap salts is formed on the frictional interface of steel substrate, with a well-ordered arrangement along the sliding direction, which dominates the contributions of the excellent lubrication.