Solvent-free microwave extraction (SFME) is a clean and advanced method of extracting essential oils. In this study, it was compared to conventional hydrodistillation (HD) and steam-water distillation (SD), which are commonly used to extract essential oils from fresh ylang-ylang flowers. The yield and density of essential oils extracted via SFME within 40 min after the appearance of the first oil drop were higher than those obtained via conventional HD and SD within 3 h after the appearance of the first drop. Analysis of chemical compounds in the essential oils showed a high degree of variability in volatile compounds between the three extraction methods. Light oxygenated compounds are odor-active constituents. They comprised 81.23% of the SFME extract, whereas their levels were lower in the HD (69.94%) and SD extracts (57.98%). Total aromatic compounds were also higher in the essential oils obtained via SFME than in those obtained via HD and SD. These results support the use of SFME for ylang-ylang essential oil extraction, as it offers promising energy-/time-saving characteristics, along with higher quality.