The roles of enzymatic (Lipoxygenases, LOX) oxidation and autoxidation in the dry-cured processing of mackerel were investigated by adding exogenous substances in this study. Four groups, namely control, chlorogenic acid (inhibiting LOX activity), EDTA-2Na (inhibiting autoxidation), and exogenous LOX (adding eLOX), were assigned. The results showed that lipid oxidation of mackerel was reduced by inhibiting LOX activity and autoxidation, while adding eLOX promoted lipid oxidation. Inhibition of LOX activity and autoxidation suppressed fatty acid accumulation mainly in the air-drying and curing stage, respectively. The total contents of key flavors in the mackerel during dry-cured processing were decreased by inhibiting LOX activity and autoxidation, and the former inhibitory effect was stronger than autoxidation, while it was corresponding increased through adding eLOX, of particular in the later stage of air-drying. Collectively, LOX could promote the flavor formation of the mackerel in the dry-cured processing, which could be applied in the flavor adjustment of aquatic products or some similar fields.