Unraveling the Aromatic Profiles of Longnan Olive Oils: A Complementary <scp>HS</scp> ‐ <scp>GC</scp> ‐ <scp>IMS</scp> and <scp>HS</scp> ‐ <scp>GC</scp> ‐ <scp>MS</scp> Analysis for Varietal Discrimination

ABSTRACT This study employed a complementary analytical approach, combining headspace gas chromatography–ion mobility spectrometry (HS‐GC‐IMS) and headspace gas chromatography–mass spectrometry (HS‐GC‐MS), to comprehensively characterize the dynamic evolution of volatile organic compounds (VOCs) in virgin olive oil (VOO) from Chenggu 32 (CG‐32) and Koroneiki (KK) cultivars across eight maturity indices (MIs). The combined strategy proved powerful: HS‐GC‐IMS detected 90 VOCs, excelling in profiling polar, aroma‐active compounds, while HS‐GC‐MS confirmed 61 VOCs, providing broader metabolome coverage. Multivariate statistical analysis revealed that genetic cultivar is the primary driver of VOCs profile divergence. The CG‐32 variety was characterized by a high abundance of aldehydes, imparting classic “green” notes, whereas the KK variety was dominated by ketones, resulting in a less traditional, intense aroma. Notably, a key finding was that genetic factors can override ripening trends, as evidenced by the late‐harvest KK sample clustering with the early‐harvest CG‐32 sample based on VOCs signature. Orthogonal partial least squares‐discriminant analysis (OPLS‐DA) models exhibited exceptional predictive power ( Q 2 &gt; 0.94) for varietal authentication, and a set of 35 key discriminatory markers (VIP &gt; 1.0) was identified. This work underscores that MIs alone is an insufficient harvest guide and establishes a robust foundational methodology for VOCs‐based quality control and varietal screening of olive oils. The high predictive power of the models demonstrates their potential for authenticity purposes, which now warrants validation with a larger sample set.