The depletion of natural oils and global environmental issues compelled the researchers to explore the feasibility to use green lubricants for industrial/commercial applications. In the present study the effect of fatty acid compositions of seven types of green oils (i.e., cottonseed, sesame, castor, olive, rapeseed, neemseed and sunflower oil), has been investigated for the tribological behaviour in close contact sliding conditions. The four-ball tester was used to evaluate the antiwear and antifriction performance of the green oils as per the ASTM D4172 standard. The fatty acid compositions (i.e., saturates and unsaturates) demonstrated the distinct role during the tribological analysis. Cottonseed oil showed a minimum wear scar diameter (i.e., 759.8 µm) at the lubricated sliding surface; on the contrary, the average coefficient of friction was highest (i.e., 0.088). Nonetheless, sunflower (873 µm) and castor (906.4 µm) oils have shown wear scars in the higher range, and a low friction coefficient was achieved. There was no direct relationship observed between the wear and friction in this study. It was observed that along with the saturation, oleic acid (C18:1) and linoleic acid (C18:2) contents also play a vital role in the tribo-performance. Gas chromatography mass spectroscopy (GC–MS) and thermogravimetric analysis (TGA) were used to estimate the fatty acid composition and thermal stability analysis of the explored green oils, respectively.