Zinc dialkyl dithiophosphate (ZDDP) is a key antiwear additive in lubricants that forms robust phosphate glass-based tribofilms to mitigate wear on rubbing surfaces. The quest to unravel the enigma of these antiwear film formations on sliding surfaces has persisted as an enduring mystery, despite nearly a century of fervent research. This paper presents a comprehensive review of nanotribological investigations, centering on the tribochemical decomposition of ZDDP antiwear additives. The core of the Review explores investigations conducted through the in situ AFM-based technique, which has been used to unveil the underlying stress-assisted thermal activation (SATA) mechanism behind the formation of antiwear tribofilms on diverse surfaces. A thorough analysis is presented, encompassing governing factors, such as compression, shear, and temperature, that wield influence over the intricate process of tribofilm formation. This is substantiated by a spectrum of structural and chemical characterization-based inferences. Furthermore, atomic-scale computer simulation studies are discussed that provide profound insights into tribochemical reaction mechanisms and elucidate the details of chemical processes at atomic level.