Abstract This study aimed to identify and compare the flavor substances in mature tomato and pepper fruits using flavoromics based on GC×GC-TOF-MS. A total of 1560 volatile substances were identified, including 627 tomato specific substances and 534 pepper specific substances. Esters were identified as the distinguishing factor in the aroma profiles of the two. ROAV, an effective flavor evaluation criterion, can help identify the main contributors to flavor that can be detected by the taste buds. VOCs with ROAV > 1 are typically regarded as the key flavor contributors. Interestingly, it was found that tomato and pepper shared three common VOCs (2-nonenal, (E)-; 2-octenal, (E)-; and furan, 2-pentyl-.), which exhibited higher ROAV in both. Except for the three common VOCs, heptanal; 2-dodecenal, (E)-; 1-octen-3-one; 2-undecanone in tomato and pyrazine, 2-methoxy-3-(2-methylpropyl)- in pepper were identified to be contributive to their corresponding aromatic flavor (ROVA > 1), respectively. The contents of 138 volatile metabolites differ between tomato and pepper. Among them, acetoin, dodecanal and 1-decanol demonstrated highest fold change (Log2FC > 10). The flavor wheel shows the most obvious flavor characteristic of both tomato and pepper is sweet flavor. In addition, green, fruity, herbal, woody and apple flavors are prominent in pepper, while waxy, citrus and fatty flavors are prominent in tomato.