Three kinds of S- and P-free borate esters containing N with different alkyl chain lengths were prepared by using boric acid, ethanolamine, and alkyl-alcohol as the starting materials. The chemical structure of the products was analyzed by means of Fourier transformation infrared spectrometry, elemental analysis, and so on. The thermal stability of the products was evaluated by thermogravimetric analysis. The tribological properties of the synthesized borate esters as lubricating oil additives in liquid paraffin were evaluated using a four-ball friction and wear tester while the morphologies of the worn scars of the steel balls were observed using a scanning electron microscope. The chemical components on the worn surfaces of the steel balls were analyzed using an X-ray photoelectron spectroscopy. Results show that all the three kinds of synthetic borate esters as additives in liquid paraffin possess good antiwear performance and may be used as promising S- and P-free environmentally acceptable lubricating oil additives. Particularly, borate ester with short alkyl chain length at a low concentration in liquid paraffin was more effective in reducing wear, and the antiwear ability of the additives decreased with increasing alkyl chain length. The antiwear ability of the N-containing borate esters as additives in liquid paraffin might be closely related to the formation of hydrogen bonds via N with a high electronegativity and small atomic radius and the easy permeation of electron-deficient B on the rubbing steel surfaces.