Wuyi Rougui tea is a kind of oolong tea made from the fresh leaves of Cinnamomum cassia(Camellia sinensis cv. Rougui), which is a provincial improved tea tree variety in Fujian Province and deeply favored by consumers because of the characterization of 'rock in the throat, flower in the mouth'. Besides fresh tea leaves, the aroma quality of Wuyi Rougui tea depend greatly on the manufacturing process. However, studies on the metabolic mechanism of aliphatic aroma components represented by green leaf volatiles (GLVs) and fruit esters during process have not been reported. Fresh tea leaves, solar-withering leaves and turn-over leaves of Wuyi Rougui tea were used as test samples. The detection of aliphatic aroma components in samples during manufacture was done by headspace solid phase microextraction (HS-SPEM) combined with gas chromatography time-of-flight mass spectrometry (GC-TOF-MS) . The aliphatic aldehydes were significantly reduced during the turn-over process, while a large amount of aliphatic alcohols and esters were formed and accumulated. Among them, leaf alcohol esters, hexenols and hexenyl esters could responded to water loss and mechanical damage, respectively. The key enzyme activities in the LOX-HPL pathway during process was detected by UV/visible spectrophotometry. The results indicated that the activities of lipoxygenase(LOX), alcohol dehydrogenase(ADH) and alcohol acyltransferases (AAT) reached their peak values in the third time(3T), the fourth time(4T) and the fifth time(5T) of turn-over process, respectively. The results of quantitative reverse transcription polymerase chain reaction(qRT-PCR) demonstrated that CsLOX2 and CsLOX5 genes had a higher relative expression levels in the initial stage of turn over (2T, 3T), and the up-regulation of relative expression of CsADH2-1 and CsAAT genes was observed during the late stage of turn over (4T, 5T) when the process advanced. The correlation between aliphatic aroma, enzyme activity and gene expression during manufacturing pocess of Wuyi Rougui tea was evaluated by Pearson coefficient. A large number of aliphatic alcohols with natural floral and fruity flavors such as 1-hexanol, cis-3-hexenyl isovalerate, hexanoic acid, hexyl ester, cis-3-hexenyl-methylbutyrate and cis-3-hexenyl salicylate, had significant(P<0.05) or extremely significant(P<0.01) positive correlation with the CsADH2-1 gene. Meanwhile, CsAAT gene had similar expression pattern with CsLOX2 and CsLOX5 genes during manufacturing process(r=0.762，r=0.732). Co-expression of key genes in the LOX-HPL pathway drove the synthesis and accumulation of aliphatic aromas during manufacture, laying an important basis for the formation of the aroma-related volatiles of Wuyi Rougui tea.