The formation of boundary layers on bearing surfaces due to the operational conditions has a significant influence on bearing lifetimes and frictional properties. Zinc dialkyldithiophosphate is an anti-wear additive widely used in oil and grease formulations that forms beneficial surface boundary layers. Under certain circumstances, this additive can cause early bearing failure due to white etching cracks (WEC) formation. By influencing chemical reactions and diffusion processes, the boundary films are suspected to be a reason for the emergence of WECs. The properties of these layers under WEC critical and uncritical conditions are of interest. To gain knowledge of these layers, nano- and micro-tribological tests were performed. One possibility is to measure the hardness by nanoindentation and scratching on and into the layers by nano scratch tests. Another way is to perform local resolved micro-pin-on-disk tests. Additionally, ToF-SIMS (Time-of-Flight Secondary Ion Mass Spectrometry) was performed on the bearing surfaces to conclude the chemical compositions of the boundary layers. In the focus was, if the measured properties of the layers can be correlated to the bearing’s early failures due to WEC, frictional properties of the whole system, and the wear on the surfaces.