Poly-Ether-Ether-Ketone (PEEK) has been widely used for tribological applications with steel counterparts because of its superior mechanical and self-lubricating properties. Fluid lubrication has the potential to further improve the performance of PEEK/steel contacts but its effect has been shown to depend on the operating conditions. To elucidate these aspects and establish the mechanism of fluid lubrication, the friction and wear properties of the PEEK/steel contacts in both dry and poly-α-olefin (PAO) lubricated conditions were investigated by tribological tests and surface analytical techniques. The nanoindentation measurements showed that lubrication with PAO had a softening effect on the wear track of PEEK, but no correlation was established with the wear of PEEK. The tribological behavior, for both dry and lubricated contacts, was correlated with the thickness of PEEK transfer films on the steel counterparts. The thickness of these films, as determined by Electron Probe Micro Analysis (EPMA) and X-ray Photoelectron Spectroscopy (XPS), was controlled by the rates of their formation and removal and depended on the operating conditions. Moreover, lubrication with PAO inhibited not only the formation but also the removal of PEEK transfer films. This study thus sheds light on the mechanism of fluid lubrication of the PEEK/steel contacts.