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<i>Freesia hybrida</i> is a group of cultivars in the genus <i>Freesia</i> with a strong floral scent composed of diverse volatile organic compounds (VOCs). In this study, the VOCs of 34 <i>F. hybrida</i> were extracted and analyzed by headspace solid phase microextraction and gas chromatography mass spectrometry (HS-SPME-GC-MS). A total of 164 VOCs whose relative contents were higher than 0.05% were detected. The numbers of VOCs in all germplasms differed between 11 to 38, and the relative contents ranged from 32.39% to 94.28%, in which most germplasms were higher than 80%. Terpenoids, especially monoterpenes, were the crucial type of VOCs in most germplasms, of which linalool and D-limonene were the most frequently occurring. Principal component analysis (PCA) clearly separated samples based on whether linalool was the main component, and hierarchical clustering analysis (HCA) clustered samples into 4 groups according to the preponderant compounds linalool and (<i>E</i>)-β-ocimene. Comparison of parental species and hybrids showed heterosis in three hybrids, and the inherited and novel substances suggested that monoterpene played an important role in <i>F. hybrida</i> floral scent. This study established a foundation for the evaluation of <i>Freesia</i> genetic resources, breeding for the floral aroma and promoting commercial application.