In this study, molybdenum dithiocarbamate (MoDTC) coatings were fabricated on 304 stainless steel substrates via an electrodynamic spraying process with the aim to clearly understand the evolutionary process from MoDTC to MoS₂ during contact sliding. Experiments were performed using an in-situ tribo-tester equipped with Raman spectroscopy to continuously monitor the chemical state of the wear track. The tribochemical reaction and removal process of MoDTC were assessed, and the evolution process of MoDTC was determined systematically. Additionally, it was determined that the tribological performance of the MoDTC coating was dominated by a tribochemical reaction at the microscale and by surface topography at the macroscale.