<p>Ti-6Al-4V titanium alloy is prone to high temperatures and poor machinability during processing. To address this, a novel system combining supercritical CO₂ (ScCO₂) cooling and electrostatic minimum quantity lubrication (EMQL), termed ScCO₂–EMQL, was applied to its milling. This system generates a low-temperature, charged spray, significantly improving cutting zone cooling and lubrication. This study investigated how voltage, air pressure, flow rate, and nozzle distance affect the ScCO₂–EMQL spray’s charge-to-mass ratio and droplet size, as well as its heat transfer enhancement. The charge-to-mass ratio positively correlates with voltage and air pressure, but negatively with flow rate and nozzle distance. Conversely, droplet size negatively correlates with voltage and air pressure, but positively with flow rate and nozzle distance. Charged droplets under − 6&#xa0;kV improved transient heat transfer by 8.65% and steady-state heat transfer by 4.61% compared to uncharged droplets. Further milling performance studies on Ti-6Al-4V revealed that ScCO₂–EMQL reduced cutting temperatures by 51.03, 44.74, 7.21, and 1.89% compared to dry cutting, EMQL, ScCO₂, and supercritical CO₂ minimum quantity lubrication (ScCO₂–MQL), respectively. Crucially, compared to ScCO₂–MQL, ScCO₂–EMQL reduced tool flank wear by 9.5%, decreased cutting force by 13.1%, and extended tool life by 12.5%. This demonstrates ScCO₂–EMQL as a highly efficient cooling and lubrication technology.</p>