The floral headspace compounds of Chinese Rosa rugosa germplasms that were isolated by an automated headspace sampler with built-in trap, and followed by gas chromatography-mass spectrometry for identification and quantification. Up to 33 volatile compounds were identified from the 23 rose germplasms, including nine alcohols, five esters, three alkanes, 10 terpenes, three aldehydes, two ketones, and one ether. The main floral components identified were 2-phenylethanol, β-citronellol, ethanol, and n-hexane. 'xizi', 'miaofengshan', 'xiangciguo', and 'tangbai' contained the highest amounts of 2-phenylethanol at 84.66 μg·g⁻¹, β-citronellol at 70.98 μg·g⁻¹, ethanol at 83.87 μg·g⁻¹, and n-hexane at 18.23 μg·g⁻¹, respectively. 'Rongchengyesheng', 'tanghong', 'xizi', 'miaofengshan', and 'baizizhi' could be considered good materials for extracting rose oil and breeding new cultivars.