•Fenile, Ginestra, Pepella, and Ripoli autochthonous grapes were chemically characterized.•Phenolics, amino acids and oleanolic acid were analyzed by NMR, LC-MS and HPLC.•Chemical characterization of grapes will serve as a tool of variety differentiation.•Chemical characterization of grapes will help wineries to ameliorate their wines. Minor grape varieties often possess key traits to produce wines with specific territorial identity. Italy is home to a wide selection of autochthonous grapevines. In 2005, four white grape varieties from the Amalfi coast, Fenile, Ginestra, Pepella and Ripoli were registered in the National Catalogue grapevines. They are all complementary varieties with a rich biodiversity and linked to an ancient wine heritage. Studies on such varieties have not been conducted yet. Here, the metabolite content of the above four grape varieties is described. Ripoli was the richest in quercetin derivatives while very low was the content of kaempferol derivatives; Pepella possessed an equal amount of quercetins and kaempferols; Ginestra and Fenile featured a quercetins abundance twice that of kaempferols. Also, the (+)-catechin content was higher than (–)-epicatechin's; B-type procyanidins occurred in higher concentrations in Pepella and Ripoli than in Fenile and Ginestra. Hydroxycinnamic acids were also identified and quantified. Seeds from each variety were carefully analyzed and flavanols were identified up to decamers along with their galloylation percentage. The obtained data are a tool of variety differentiation and useful to develop appropriate vinification procedures to ameliorate the quality of wines.