The Italian wine appellations system is organized in hundreds of origin wines, with unique characteristics that are protected with many denominations of origin. The aim of this work was to analyze and compare the proanthocyanin profile of 12 single-cultivar and single-vintage Italian red wine groups (Aglianico from Campania, Cannonau from Sardinia, Corvina from Veneto, Montepulciano from Abruzzo, Nebbiolo from Piedmont, Nerello Mascalese from Sicily, Primitivo from Apulia, Raboso Piave from Veneto, Sagrantino from Umbria, Sangiovese from Tuscany and Romagna, and Teroldego from Trentino), each one produced in their terroirs under ad hoc legal frameworks to guarantee their quality and origin. All wines were analyzed with a protocol that combined the phloroglucinolysis reaction with an LC-MS/MS instrument. The results underlined Sagrantino wines as the richest in proanthocyanins. Sangiovese, Montepulciano, Nerello, and Teroldego were the richest in B-ring trihydroxylated flavan-3-ols, and especially Nerello was the richest in prodelphinidins. Cannonau, Raboso Piave, Nerello, and Corvina were characterized by C-ring trans conformation flavan-3-ols. Nebbiolo and Corvina had high percentages of galloylated flavan-3-ols. Aglianico and Primitivo had the lowest percentages of B-ring trihydroxylated and C-ring trans conformation flavan-3-ols. This information should be useful in better understanding the Italian red wines and valorize them.