The optimal process conditions for solvent-free microwave extraction(SFME) of essential oils from Cinnamomum longepaniculatum deciduous leaves after moisture conditioning were established by response surface methodology(RSM). A Box-Behnken design(BBD) was applied to evaluate the effects of three independent variables: moisture content(A: 54%–74%), microwave power(B: 300–500 W) and microwave time(C: 20–40 min), on the extraction yield of essential oil. The compounds of the essential oils obtained by SFME, hydro-distillation and microwaveassisted hydro-distillation(MADE) were identified by gas chromatography-mass spectrometry(GC-MS), and the total lipids of C. longepaniculatum fresh leaves and deciduous leaves were analyzed. The correlation analysis of the response regression model indicated that quadratic polynomial model could be employed to optimize the extraction of essential oil. The optimal extraction condition was A: 58%, B: 400 W and C: 28 min. In the optimal condition, the maximum extraction yield was 4.475 m L/100 g dw and higher than that by MADE. The main compound of the essential oil was eucalyptol(63.54%), and total oxygenated compounds was 78.95%, mainly caused by SFME and the metabolism of endophytic bacteria with decreasing content of phospholipids and fatty acids. Analysis of variance under the extraction condition illustrated high fitness of the model and the success of RSM for optimizing and reflecting the expected process condition. SFME combined with moisture regulation was an effective method for extracting essential oil from C. longepaniculatum deciduous leaves.