Litsea cubeba fruit, which has the highest content of essential oils in the plant, is an important woody oil plant resource. In this study, the influence of the solvent-free microwave extraction (SFME) and hydrodistillation (HD) techniques on the extraction of L. cubeba fruit essential oils was investigated in terms of yield, kinetics, and chemical composition, where the former conditions were optimized by the response surface design. The maximal essential oil yield was obtained under the optimal SFME process conditions (442 W and 24 min), where the irradiation time was the most important variable (p < 0.0001). Regardless of the extraction method used, the influence of harvesting time on L. cubeba fruit essential oils were quantitatively and qualitatively analyzed afterwards, where the SFME essential oil from July showed its superiority over the others regarding its higher extraction yield and better bioactivities. Compared with the HD method, the SFME approach could significantly enhance the yield of essential oils extracted from June to August by nearly 47% with the advantages of saving energy and low environmental impact. Interestingly, the SFME method could selectively extract monoterpene hydrocarbons such as D-limonene with relation to different compositions and bioactivities. Moreover, SFME essential oil showed a better inhibitory effect on tyrosinase and melanogenesis, indicating its skin-whitening potential as a new promising natural cosmetic ingredient.