In surface engineering, new coatings and deposition techniques for decreasing wear have been proposed. However, the tribological behaviors of these coatings under lubricated sliding with biodegradable oils are unknown. The objective of this study was to evaluate the tribological behaviors of two hydraulic biodegradable oils, namely hydraulic environmental ester oil synthetic (HEES) and hydraulic oil environmental polyalphaolefin (HEPR), with hydraulic mineral oil (HLP), using a pin-on-disk tribometer. In the sliding tests, a Cu-35Zn sphere against a flat surface is coated with WC-10Co4Cr alloy using a HVOF thermal spray. The Stribeck curve was used to evaluate the performances of the lubricants. The coefficient of friction, the contact pressure, and the film thickness were determined. In addition, the coefficient of wear of the sphere was evaluated, and the oil with the lowest value was identified, which was HEPR in this case. In long-term tests, HEPR was affected by the stick-slip phenomenon, which increased the coefficients of friction and wear. Furthermore, the mechanism of adhesion of the sphere on the disk was more evident with the use of HEES compared to HLP. The highest concentrations of Zn and P and the pressure-viscosity coefficient value, which was detected in the mineral oil, caused friction reduction and lower damage to the surfaces. Therefore, it is important to evaluate the tribological conditions of synthetic bio-lubricants for applications in hydraulic systems.