Modern day industrial applications involve rigorous operating conditions, which include high temperature, heavy applied loads, and starved lubrication conditions. In these scenarios, either the lubricant slips out of the contact or only a thin layer of lubricant resides between interacting surfaces. The deposition of diamond-like carbon (DLC) coatings possessing extreme wear resistance and ultra-low friction characteristics and using lubricants capable of physically adsorbing on the interacting surfaces can significantly improve the tribological performance. Due to their superior tribological characteristics, chemically modified vegetable oils, such as palm trimethylolpropane ester (TMP), are one of the potential candidates to be used as lubricant base-oils. To prove the suitability of TMP and DLC coatings for applications involving a boundary-lubrication regime, a logical step forward is to investigate their tribological characteristics in combination with conventional lubricant additives. In this study, the extreme pressure characteristics of TMP formulated with glycerol monooleate (GMO), molybdenum dithiocarbamate (MoDTC), and zinc dialkyldithiophosphate (ZDDP) in combination with steel/steel contact were investigated using a four-ball wear tester. In addition, the tribochemical compatibility of the abovementioned additives with TMP and a tungsten-doped diamond-like carbon coating (W-DLC) was also analyzed using a universal wear testing machine. For comparison, additive-free and formulated versions of polyalphaolefin (PAO) were used as a reference. Moreover, various surface characterization techniques were used to investigate the mechanisms responsible for a particular tribological behavior. TMP-based lubricants exhibited superior extreme pressure characteristics and friction performance as compared to those containing PAO. An improvement in the tribological performance was observed when W-DLC-coated surfaces were used instead of uncoated-surfaces irrespective of the lubricant formulation.