The tribological behavior of traditional oil-in-water (O/W) lubricants (1.0 wt.%) and nano-TiO2 additive lubricants (1.0–9.0 wt.%) during micro rolling of titanium foils were analyzed. In this study, the surface morphologies of titanium foils under various lubrication conditions were assessed, and the corresponding lubrication mechanisms were revealed. The tribological behavior of nano-TiO2 additive lubricants during micro rolling of titanium foils was also explored through a series of characterization methods. The utilization of nano-TiO2 additive lubricants in micro rolling reduces the surface roughness of titanium foils. Moreover, it effectively inhibits the generation of indentations and cracks during rolling processes, enhancing the surface quality of rolled specimens. Additionally, owing to the synergism of rolling, tribo-film, mending and polishing effects of the nanoparticles, both the rolling force and surface roughness were minimized by using lubricants containing 3.0 wt.% TiO2 nanoparticles. Overall, an optimal concentration (3.0 wt.%) of TiO2 nanoparticles in water-based nanolubricants was obtained with enhanced tribological properties and lubrication performance during micro rolling of titanium foils.