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Water-based lubrication, due to the poor film-forming ability of water, faces challenges in achieving effective lubrication for titanium alloys. This study systematically investigates the frictional performance of phosphorus-based extreme pressure (EP) additives and self-emulsifying esters (SEE) on the surface of titanium alloy (TB6) under different pressures and temperatures. The core lubricant consists of SEE with nonylphenol polyoxyethylene ether phosphate ester (NPEP), polyoxyethylene oleyl ether phosphate ester (POEP), and alcohol ether phosphate ester (AEP). Results show that SEE significantly improves the film-forming ability of the aqueous solution, while phosphate ester forms a strong chemical adsorption film on the alloy surface via P-O-Ti covalent bonds, enhancing the strength of the lubricating film. The combination of SEE and phosphate esters in the water-based solution enables effective lubrication for titanium alloys. Particularly, the mixture of POEP and SEE demonstrates excellent synergistic effects, making it an ideal blend for water-based cutting fluids for titanium alloys. This study elucidates the lubrication mechanisms and action ranges between different additives, providing important guidance for the development and promotion of water-based cutting fluids.