A better understanding about the rolling contact fatigue and micropitting performance of machine component surfaces lubricated with environmentally friendly lubricants is critical to designing and further formulating new lubricants intended to be used in rolling–sliding contacts such as those found in gear and bearing applications. In this work, the frictional behaviour and rolling contact fatigue (RCF) performance of DLC, Cr/a-WC:H/a-C:H and a-C:Cr coatings under glycerol-based lubrication in rolling sliding contact conditions have been investigated. Traction maps, Stribeck curves, and fatigue plots have been generated by using a micropitting test rig (MPR). The initiation and progression of micropitting was monitored by means of white light optical interferometry and scanning electron microscopy (SEM). Results indicated that glycerol-based lubricants exhibited a significant friction reduction as the hydrodynamic effect is enhanced at higher rolling-speeds. Under boundary lubrication the friction coefficient was significantly higher compared to the values obtained with a commercial mineral-based transmission oil. Compared to uncoated steel surfaces, DLC coatings effectively reduced the volume loss and micropitting progression. Irrespective of the coating thickness, DLC showed an excellent tribological behaviour when the base lubricant favours the onset of mild-wear, over micropitting. When the lubricant formulation favoured the onset of micropitting, the coatings tended to prematurely fail due to debonding from the substrate, and local micro-spallation. The experiments demonstrated that friction reduction does not necessarily correspond with a reduction of micropitting.