Nanodiamonds are known to improve tribological performance when added to lubricants, but their impact on additives that may already be present in the lubricant is poorly documented. Here, we report on a study of their effects on thermal reaction films formed from tricresyl phosphate (TCP) on Fe substrates immersed in a dibasic ester basestock when blended with TCP. Thermal reaction film formation temperatures were recorded in-situ by monitoring the reaction film formation on both Fe and air baked Fe surfaces using a quartz crystal microbalance (QCM). The nanodiamonds were found to raise the thermal reaction film formation temperature by 18 °C, possibly by raising the activation energy for the reaction, but they were not observed to affect the thickness or rate of formation of the films. The nanodiamonds, moreover, were observed to trigger thermal reaction film formation on air baked Fe surfaces that otherwise were highly resistance to reaction film formation. The surface morphology, roughness, and thickness of the thermal reaction films, as measured by atomic force microscopy (AFM), are reported as well as their chemical compositions, as studied with Electron Dispersive X-ray Spectroscopy (EDS). The coefficients of friction measured on the thermal reaction films during dry solid–solid contact are also reported.