Owing to the requests of exploring environment-friendly and multifunctional lubricant additives, three novel imidazoline-type thiadiazole derivatives are prepared and used as lubricant additives in two biodegradable base stocks, colza oil and synthetic diester, respectively, and their tribological performance is tested using the four-ball tester. For further understanding of their tribological behaviors, x-ray absorption near edge structure (XANES) spectroscopy is adopted to analyze the thermal films and tribofilms generated from these additives in two base stocks. Tribological tests show that all these thiadiazole derivatives are effective in reducing wear in synthetic diester, and derivative SIB (stearic acid-imidazoline-type thiadiazole derivative) is better than derivative OIB (oleic acid-imidazoline-type thiadiazole derivative) and derivative DIB (lauric acid-imidazoline-type thiadiazole derivative) in reducing friction at high additive concentrations. But these derivatives almost fail in improving the tribological characteristic of colza oil. According to XANES spectra, thermal films formed in two base stocks are mainly composed of ferrous sulfate and adsorbed organic sulfide. These derivatives are also easily oxidized into high-valent sulfate in colza oil during the rubbing process, and ferrous sulfate is the main component of these tribofilms. But in synthetic diester, tribofilms are mainly composed of ferrous sulfide, and it is notable that the tribofilm generated by derivative SIB at 1.0 wt. % is composed of ferrous sulfide and ferrous disulfide. Under extreme-pressure conditions, these derivatives easily react with the metallic surface to generate ferrous sulfide in colza oil. But in synthetic diester, adsorbed organic sulfide is the main component of those films. The base stock has a great impact on the compositions of these reaction films, so the tribological behaviors of these derivatives are different in two base stocks.