The production process conditions of vinegar from fresh potatoes were studied through simultaneous saccharification and fermentation and acetic fermentation. The influence of factors on total acid content was also studied according to Central Composite Design based on the single factor tests. The results showed that the optimal parameters of the fermentation were with inoculum size 12 mL/100 mL, processing at 34 ℃ for 6 d. Under this condition, the total acid content reached 3.21 g/100 mL, and the vinegar showed amber color and moderate sourness. Moreover, 14 kinds of flavor substances such as eugenol, benzene alcohol and phenethyl acetate were also detected by using HS-SPME/GC-MS in this study.