Grape skin, seed and flesh, a potential source of bioactive compounds, were investigated to discriminate Kyoho skin, seed and flesh antioxidant activities by solvent extraction using chemometrics, including multivariate, discriminant analysis (DA) and hierarchical cluster analysis (HCA). Multivariate analysis (Wilk's Λ = 0.02 × 10‐4, P < 0.01) explained the discrimination behaviour of phenolics and antioxidants by different solvents. Moreover, DA with three discrimination functions (DFs) and HCA with three well‐defined clusters (clusters 1 to 3) further demonstrated the differences and/or similarities among the solvents. Solvent I (75% ethanol: water) exhibited the different extraction process over the solvents IV (water) and III (acetone: water). Quercetin (39.25 mg kg−1), epicatechin (53.08 mg kg−1) and gallocatechin gallate (1.28 mg kg−1) were the major phenolic compounds in Kyoho skin, seed and flesh extracts, respectively. These further confirmed the chemometric approach that could be used to discriminate solvents. Therefore, these findings suggested the application of chemometrics in extraction studies to understand the role of solvents and high recovery of grape bioactive compounds.