Since ancient times, lubricants have been used to reduce friction and wear problems of mechanical systems. However, nowadays, there is a constant effort to improve their performance through additives so that they can accomplish properly in this modern world. In that sense, in this study, it was proposed the use of Poly(ε-Caprolactone) (PCL) as a biodegradable additive in Castor oil. The effect that this additive has on the tribological properties of AISI 4140 steel/Al2O3 tribosystem was analyzed. For this purpose, PCL was dissolved in Castor oil at 65 °C for 15 minutes. Later, once the lubricant formulations got into room temperature, friction tests were conducted with a ball-on-disk configuration. Several experiments were systematically carried out in order to study the factors that could influence the performance of the tribological system, for instance: additive concentration, velocity, temperature, and wear track radius. The kinetic friction coefficient was used to analyze the results as an output variable. The parameters in which the best friction behavior was observed were employed again to compare the efficiency of the polymeric additive by profoundly analyzing and comparing the wear response of the system. The PCL additive showed great results by decreasing friction up to 30% compared to the neat Castor oil. Nevertheless, as the opposite effect, this additive increased the steel wear to almost half an order of magnitude. Given the above, this investigation showed that, with further studies, Poly(ε-Caprolactone) could be used as an additive in vegetable oil-based lubricants for the improvement of friction performance.