Exhaust gas recirculation (EGR) is widely used in diesel engines to reduce nitrogen oxide (NOx) emissions. However, a lacquer is formed on the EGR valve or EGR cooler due to particulate matter and other components present in diesel exhaust, causing serious problems. In this study, the mechanism of lacquer deposition is investigated using attenuated total reflection Fourier transform infrared spectrometry (ATR-FTIR) and scanning electron microscopy (SEM). Deposition of temperature-dependent lacquers was evaluated by varying the temperature of a diamond prism between 80 and 120 °C in an ATR-FTIR spectrometer integrated into a custom-built sample line, which branched off from the exhaust pipe of a diesel engine. Lacquers were deposited on the diamond prism at 100 °C or less, while no lacquer was deposited at 120 °C. Time-dependent ATR-FTIR spectra were obtained for approximately 2 h from the beginning of the experiment. When the engine was started, water was detected during the initial period for all temperatures used. After the evaporation of water, spectra of aromatic hydrocarbons were observed at lower temperatures, while C=O absorption peaks were observed in the case of higher temperatures. Images of the lacquer obtained by SEM showed the presence of soot in the lacquer. These experimental results formed the basis for the elucidation of the lacquer formation mechanism.