In order to investigate the volatile oil composition of Valeriana officinalis L. var. latifolia Miq. and its variability in 12 main origins. In this study, the electronic nose technique was used for the preliminary detection of the volatile constituent categories of VRR; the solid-phase microextraction-gas chromatography-mass spectrometry (SPME-GC-MS) technique was used for detailed compositional analysis of the volatile oils of VRR, and combined with principal component analysis (PCA), hierarchical cluster analysis (HCA) and orthogonal partial least squares discriminant analysis (OPLS-DA) for the multivariate analysis. It was found that the highest response values were determined by electronic nose for the volatile components containing nitrogen-oxygen and sulfur-containing elements, and the results of the double-labeling plot indicated that the strongest correlation between nitrogen-oxygen containing compounds and sulfur-containing volatile components with T5 (Dewang Town, Jiangkou County, Guizhou Province). A total of 80 volatile components were identified by SPME-GC-MS, among which the maker components and the highest relative contents of lobyl acetate (22.99%-54.55%) were found. The PCA and HCA analyses showed that the volatile components in the 12 batches of VRR were correlated with their origins and they could be categorized into three major groups. The OPLS-DA analysis could realize the correlation between 12 VRR samples from different origins, with more obvious differences in volatile constituents in VRR samples from different origins, and screened two major differential volatiles by the value of variable importance in projection and fold change. The results of this study provide a reference for the application of VRR in the pharmaceutical and healthcare and flavor industry.