The growing sensitivity toward sustainability is being demonstrated by an increase in sales of natural wines. Natural wines are obtained using exclusively native vines, indigenous yeasts, absence of additives, irregular temperature control during fermentation, and smaller quantities of sulfites even compared to organic wines. In this work, natural wines were obtained from Fiano grape, a historical cultivar of Irpinia (Campania, Italy). The main objective of this study was to compare the chemical and sensory characteristics of natural wines produced using different vessels (10 HL): Test A: stainless steel; Test B: earthenware amphora; Test C: mulberry wood barrel; and Test D: cherry wood barrel without the use of starter yeasts and chemical additives, including sulfites. Our results show a greater concentration of higher alcohols and esters in wines obtained in amphora and wooden barrels. The results of this work reveal that the type of container influences the composition of wine to an important extent. In addition, the Fiano wines obtained have a distinctive sensory profile also due to the ancestral winemaking process used, which did not involve the use of starter yeasts or technological and chemical adjuvants.