Gas compression systems in petrochemical facilities are subjected to extreme pressures, cyclic loading, and variable humidity levels, which collectively challenge the integrity of lubricating films. This study investigates the performance of ester-based lubricants, which benefit from polar molecular structures and enhanced hydrolytic stability, in forming robust boundary lubrication layers under such demanding conditions. Experiments were conducted using a pin-on-disk tribometer to simulate compressor stresses, employing polyol esters and diesters across a relative humidity (RH) range of 20% to 80%. Adhering to ASTM G99 standards, friction and wear metrics were quantified, followed by detailed characterization of the resultant films via scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier-transform infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS). The results indicate that these esters generate denser and more ordered films in humid environments, achieving up to 30% wear reduction relative to conventional mineral oils. Complementary molecular dynamics (MD) simulations corroborate these observations, illustrating enhanced adhesion of ester functional groups to metallic substrates in the presence of moisture. These insights underscore the potential of humidity as a beneficial factor in lubrication efficacy, informing the development of optimized formulations for severe industrial applications. Such advancements could extend equipment service life, minimize downtime, and promote environmentally sustainable alternatives. Future efforts should prioritize field validations and formulation refinements for operational deployment.