The behavior of four phosphate ester additives with varying levels of phosphorus concentrations (very high, high, medium, and low) was examined through the course of drilling a Ti-6Al-4V titanium alloy at a constant metal removal rate (4.2 mm3/s). Cutting fluid (CF) additives were evaluated using torque, specific cutting energy (SEC), and tool wear. The drilling conditions employed had a significant influence on the performance of the phosphate ester additives. At 0.105 m/s and 0.188 m/s, the phosphate ester with very high phosphorous levels possessed the lowest SCE and torque values. The high-phosphorous-level phosphate ester displayed enhanced drilling performance at 0.293 m/s. At 0.419 m/s, the SCE and torque performance of the medium-phosphorous-level phosphate ester was preferable. The drilling performance of the phosphorus esters was observed to be related to the working mechanisms of the additives, which, in turn, was associated with the formation of a phosphorus-rich tribolayer and an organophosphate tribolayer on the cutting blade.