Lubricating materials for highly reactive titanium alloys are not sufficiently abundant, limiting their wide practical applications. In this work, the tribological properties for various lubricants on titanium alloy surfaces are investigated, as well as their physicochemical and adsorption properties in terms of structural composition. The results indicated that high polarity, long alkyl chain length and small spatial site resistance will be positively correlated with the tribological properties. The FIB-TEM analysis further illustrates that the film-forming mechanism of strong polar adsorption and tribo-chemical reaction is vital to high-performance lubricants on titanium alloys. This work shows great instructive significance to investigate the tribological properties and interaction mechanisms on titanium alloy surfaces from the perspective of molecular design.