Volatile flavor of edible oils is an important quality index and factor affecting consumer choice. The purpose of this investigation was to characterize virgin Camellia oleifera seed oil (VCO) samples from different locations in southern China in terms of their volatile compounds to show the classification of VCO with respect to geography. Different samples from 20 producing VCO regions were collected in 2020 growing season, at almost the same maturity stage, and processed under the same conditions. Headspace solid-phase microextraction (HS-SPME) with a gas chromatography–mass spectrometer system (GC–MS) was used to analyze volatile compounds. A total of 348 volatiles were characterized, including aldehydes, ketones, alcohols, acids, esters, alkenes, alkanes, furans, phenols, and benzene; the relative contents ranged from 7.80–58.68%, 1.73–12.52%, 2.91–37.07%, 2.73–46.50%, 0.99–12.01%, 0.40–14.95%, 0.00–27.23%, 0.00–3.75%, 0.00–7.34%, and 0.00–1.55%, respectively. The VCO geographical origins with the largest number of volatile compounds was Xixiangtang of Guangxi (L17), and the least was Beireng of Hainan (L19). A total of 23 common and 98 unique volatile compounds were detected that reflected the basic and characteristic flavor of VCO, respectively. After PCA, heatmap and PLS-DA analysis, Longchuan of Guangdong (L8), Qingshanhu of Jiangxi (L16), and Panlong of Yunnan (L20) were in one group where the annual average temperatures are relatively low, where annual rainfalls are also low. Guangning of Guangdong (L6), Yunan of Guangdong (L7), Xingning of Guangdong (L9), Tianhe of Guangdong (L10), Xuwen of Guangdong (L11), and Xiuying of Hainan (L18) were in another group where the annual average temperatures are relatively high, and the altitudes are low. Hence, volatile compound distributions confirmed the differences among the VCO samples from these geographical areas, and the provenance difference evaluation can be carried out by flavor.