Solid lubricants such as polytetrafluoroethylene (PTFE) are used in rolling-element bearings (REBs) when conventional lubrication (i.e. by fluids or greases) cannot be applied owing to extreme operating conditions (e.g. high temperatures or vacuum). Often a double transfer film mechanism is used with a cage acting as a lubricant reservoir resupplying the REB with solid lubricant by cage wear. An increase in service life of such bearings requires a better understanding of the transfer processes in the sliding and rolling contacts. Here, we investigate the effect of PTFE resupply on friction and lubricant film formation in a steel/steel and steel/glass rolling contact by tribometry and classical molecular dynamics (MD). A ball-on-disk tribometer is enhanced by a pin-on-disk sliding contact that transfers PTFE to the disk. The experiment allows simultaneous in situ measurement of friction and film thickness by white light interferometry in the rolling point contact. Increasing the pin load results in an increased PTFE film thickness in the rolling contact accompanied by a significant decrease in friction. To elucidate the observed film transfer and friction mechanism, sliding MD simulations with a newly developed density-functional-based, non-reactive force field for PTFE-lubricated iron oxide surfaces are performed. A strong adhesion of PTFE chains to iron oxide drives transfer film formation, while shear-induced chain alignment within PTFE results in reduced friction. The simulations reveal an anti-correlation between PTFE film thickness and friction coefficient – in agreement with the experiments. These investigations are a first step towards methods to control PTFE transfer film formation in REBs.