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Camellia oil is widely recognized as a high‐quality culinary oil in East Asia for its organoleptic and health‐promoting properties, but its chemical composition and thermal stability have not been comprehensively defined by comparisons with other oils. In this study, the triacylglycerols (TAGs) in camellia, olive, and six other edible oils were profiled by the liquid chromatography‐mass spectrometry (LC‐MS)‐based chemometric analysis. Besides observing the similarity between camellia oil and olive oil, TAG profiling showed that OOO, POO, and OOG (O: oleic acid, P: palmitic acid, and G: gadoleic acid) can jointly serve as the identity markers of camellia oil. Thermal stability of virgin camellia oil (VCO) was further evaluated by extensive comparisons with virgin olive oil (VOO) in common lipid oxidation indicators, aldehyde production, and antioxidant and pro‐oxidant contents. The results showed that p‐anisidine value (AnV) was the sensitive lipid oxidation indicator, and C9‐C11 aldehydes, including nonanal, 2‐decenal, 2,4‐decadienal, and 2‐undecenal, were the most abundant aldehydes in heated VCO and VOO. Under the frying temperature, heated VCO had lower AnV and less aldehydes than heated VOO. Interestedly, the VCO had lower levels of pro‐oxidant components, including α‐linolenic acid, free fatty acids, and transition metals, as well as lower levels of antioxidants, including α‐tocopherol and phenolics, than the VOO. Overall, great similarities and subtle differences in TAG and aldehyde profiles were observed between camellia and olive oils, and the thermal stability of camellia oil might be more dependent on the balance among its unsaturation level, pro‐oxidant, and antioxidant components than a single factor. [ABSTRACT FROM AUTHOR]