Rosa chinensis cultivars with volatile aromas are important resources in the perfume industry. The four rose cultivars introduced to Guizhou province are rich in volatile substances. In this study, volatiles from four Rosa chinensis cultivars were extracted using headspace-solid phase microextraction (HS-SPME), and analyzed with two-dimensional gas chromatography quadrupole time of flight mass spectrometry (GC × GC-QTOFMS). A total of 122 volatiles were identified; the main compounds in these samples were benzyl alcohol, phenylethyl alcohol, citronellol, beta-myrcene and limonene. A total of 68, 78, 71, and 56 volatile compounds were identified in Rosa ‘Blue River’ (RBR), Rosa ‘Crimson Glory’ (RCG), Rosa ‘Pink Panther’ (RPP), and Rosa ‘Funkuhr’ (RF) samples, respectively. The total volatile contents were in the following order: RBR > RCG > RPP > RF. Four cultivars exhibited similar volatility profiles, with alcohols, alkanes, and esters as the major chemical groups, followed by aldehydes, aromatic hydrocarbons, ketones, benzene, and other compounds. Alcohols and aldehydes were quantitatively the two most abundant chemical groups that included the highest number and highest content of compounds. Different cultivars have different aromas, and RCG had high contents of phenyl acetate, rose oxide, trans-rose oxide, phenylethyl alcohol and 1,3,5-trimethoxybenzene, characterized by floral and rose descriptors. RBR contained a high content of phenylethyl alcohol, and RF contained a high content of 3,5-dimethoxytoluene. Hierarchical cluster analysis (HCA) of all volatiles showed that the three cultivars (RCG, RPP, and RF) had similar volatile characteristics and were significantly different from RBR. Differential metabolites among cultivars were screened based on the OPLS-DA model, and there were six main enriched pathways of differential metabolites: biosynthesis of secondary metabolites, monoterpenoid biosynthesis, metabolic pathways, limonene and pinene degradation, sesquiterpenoid and triterpenoid biosynthesis, and alpha-linolenic acid metabolism. The biosynthesis of secondary metabolites is the most differential metabolic pathway.