To investigate the effect of combined high-voltage electrostatic field (HVEF)-ozone thawing on the quality of frozen pork, we compared the effects of thawing in a refrigerator at 4 ℃ with the assistance of HVEF (10 mA and 4000 V), ozone treatment (64.5 mg/m³ for 30 min) and their combination on the total plate count, moisture content, thawing loss, color, texture, microstructure, total volatile basic nitrogen (TVB-N) content, thiobarbituric acid reactive substances (TBARS) value, and volatile flavor compounds of frozen pork using fresh pork as a control. Frozen pork treated by HVEF combined with ozone showed the shortest thawing time of 2 h. The combined treatment significantly reduced the microbial load, thawing loss, TVB-N content, and TBARS value of pork, effectively inhibited the formation of metmyoglobin and fat oxidation, and maintained the color, water retention, texture properties and muscle structure integrity. In addition, this synergistic treatment altered the composition of volatile flavor substances by increasing the relative contents of aldehydes, alcohols, and alkenes, and produced several new flavor substances, mainly alcohols and ketones, which contributed significantly to the overall flavor formation of pork after thawing. In conclusion, HVEF-ozone thawing has significant advantages with regard to thawing efficiency, physicochemical indices and volatile flavor substances.