Volatile organic compounds (VOCs) in plants are various organic compounds with small molecular weight and high vapor pressure. The metabolomics approach was recently introduced to analyze VOCs involved in biological processes, such as abiotic and biotic stresses, spatial and temporal distribution, and genotypic differences. In addition, this approach is widely used in combination with identification of VOCs analysis and statistical analysis using multivariate analysis, such as principal component analysis (PCA), partial least squares-discriminant analysis (PLS-DA), hierarchical cluster analysis (HCA), etc. First, in this review, the current condition of the metabolomics approach to analyze VOCs synthesized in plants using head space-solid phase microextraction coupled with gas chromatography-mass spectrometry (HS-SPME-GC-MS) is discussed. In addition, metabolomics approach, such as extraction and analysis of VOCs using HS-SPME-GC-MS, conversion, and processing of mass spectral (MS) data, a database for VOCs identification, useful statistical methods, and statistical tools and applications, are explained. Finally, multi-omics in combination with other omics techniques, such as genomics, transcriptomics, etc. are suggested as prospects of a metabolomics approach for VOC analysis in floricultural plants using HS-SPMEGC- MS. Therefore, the metabolomics approach of HS-SPMEGC- MS will facilitate our understanding of VOCs synthesized in plants. Furthermore, the multi-omics approach will help understand gene functions involved in the biosynthesis of VOCs and help develop new development cultivars with nicer floral scents by contributing to the development of the floricultural industry.