This study primarily investigated the effects of different natural antioxidants (ascorbic acid, rosemary extract, PostbioYDFF-3 (R), and NatuProtec (R)) on changes in the lipid profiles and volatile flavors of pork chip snacks (PCS) during storage via lipidomic techniques and SPME-GC-MS. Compared with the control, the PCS containing different natural antioxidants exhibited obvious reductions in TBARS, peroxide, and acid values after 90-day storage (P < 0.05). At the initial (0 d), middle (45 d), and final (90 d) stage, 30, 32, and 50 volatile compounds and 692, 937, and 1095 lipid molecules were detected, respectively, mainly enriched in the sphingolipid pathway. The lipid hydrolysis of PCS occurred obvious with storage. Correlation analysis revealed that the rosemary extract exhibited the most optimal prevention of oxidative rancidity and maintained the superior quality profiles of the PCS during long-term storage. The present work provided a theoretical basis for the retardation of lipid oxidation during PCS storage.