This study used headspace solid-phase microextraction-gas chromatography–mass spectrometry and multivariate statistical analysis to comprehensively analyze the volatile components in Liupao tea samples throughout fermentation. In total, 1009 volatile organic compounds were detected and identified, including terpenoids, heterocyclic compounds, esters, ketones, hydrocarbons, alcohols, aromatics, and acids. Principal component and hierarchical cluster analyses, characterize the volatile components of Liupao tea samples were characterized at various fermentation stages. Orthogonal partial least squares discriminant analysis identified 248 differentiating compounds (VIP ≥ 1, P < 0.05, and |Log2FC| ≥ 1.0) during fermentation. K-means clustering analysis showed that 11 metabolites increased significantly throughout the fermentation process, whereas 31 metabolites decreased continuously. Annotation of these differential compounds revealed significant changes in sensory flavor characteristics in “green, sweet, fruity, floral, and woody” flavors. The results demonstrated significant variations in the volatile components of Liupao tea fermentation, along with notable changes in flavor characteristics.