In order to characterize the component differentiation from unripe and ripe Zizyphus jujuba var. spinosa,the approach of mass spectrometric technology was adopted to make the coupled chemometric analysis in this experiment.Firstly,the ultra performance liquid chromatography tandem time-of-flight mass spectrometry (UPLC-Q-TOF-MS/MS) technology was utilized to identify the main components from the unripe and ripe fruits.In addition,32 of the primary and secondary metabolites from the two forms of fruits were characterized,and they were classified into 5 kinds of structures.Next,primary metabolites and secondary metabolites from these two forms of fruits were clustered and their varied components were derived via the principal component analysis (PCA).According to PCA analysis,the samples were divided into two categories and 10 of components were selected as the candidate variables to differentia those two forms of fruits.Then,the candidate components from the primary metabolites to secondary metabolites were enriched in their metabolite pathways and biosynthetic pathways via KEGG (Kyoto Encyclopedia of Genes and Genomes) pathway enrichment analysis.At the same time,the candidate components were determined by a mass spectrometry multiple reaction detection (MRM) based methodology.With a good linear relationship from 0.002 3 to 800.00 μg/mL (r<0.99),the average recoveries were 96.38%-104.15% with the RSDs of 1.16%-2.46% (n=6).According to the established methodology,the effects related components from two growing periods of Zizyphus jujuba var. spinosa were oleanolic acid and jujuboside B,which involved in triterpenoids pathways;the flavor-related components were catechin and epicatechin,which involved in flavonoids pathways.