This paper studies the tribological behavior of three fatty acid anion-based ionic liquids: methyltrioctylammonium octanoate ([N8881][C8:0]), methyltrioctylammonium laurate ([N8881][C12:0]) and methyltrioctylammonium palmitate ([N8881][C16:0]) used as additive at 0.5, 1 and 2 wt% in an ester base oil. The tribological experiments were performed in two different tribometers: a Bruker UMT-3 using a reciprocating “ball-on-disc” configuration for pure sliding tests and a Mini Traction Machine (MTM) for rolling/sliding tests. After sliding tests, the wear scar was analyzed by scanning electron microscopy with energy dispersive spectroscopy (SEM-EDS) and X-ray photoelectron spectroscopy (XPS). Sliding tests results showed both friction and wear reduction of the mixtures with respect to the ester only at 25 °C. The worse tribological behavior at 100 °C could be attributed to the moderate thermal stability of these ionic liquids. Under rolling/sliding conditions, samples displayed similar antifriction and ECR behavior than the base oil at high speeds, changing to a higher friction and lower ECR at low speeds and increasing temperatures. EDX analysis showed mainly the steel disc elements. The XPS oxygen signal showed higher amount of CO bond on the worn surface after reciprocating tests at 25 °C, which could be attributable to IL-surface interaction and can explain the better wear reduction performance.