The quality of the Colli Albani volcanic soils has certainly contributed to the vine cultivars hence the name of one of the oldest wines (i.e., Alban wine). The alkali up to 15 wt%, SiO2 ≤ 52 wt% and the emplacement at high temperature (≤ 600 °C) are the bedrock features that have deeply influenced the soil-forming processes in the vineyards. However, the peculiar features of the Colli Albani soils are not well known. Field survey and textural, mineralogical, and chemical data obtained with SEM, EMP, XRD, and ICP-OES were used to characterize the vineyard soils of the Colli Albani. Leucite (Lct)-bearing soils and quartz (Qz)-bearing soils occur in the studied vineyard. The Qz-bearing soils represent more weathered volcanic material, depleted in primary minerals and enriched in clays, which show a lower cation exchange capacity (CEC) than the Lct-bearing soils. CEC is a misleading definition for the Colli Albani soils because the base cation mobility in the vineyard is independent from clay mineral enrichment in the soil. Actually, the release of K, Na, Ca, and Mg depends by (i) the complete dissolution of leucite and analcime, (ii) the oxy-reaction affecting the phlogopite, which releases K + Mg, and (iii) the incongruent dissolution of clinopyroxene characterized by the “gothic texture.” This texture highlights the capacity of clinopyroxene to release Ca and Mg in volcanic soils. Quantification of the texture and abundance of the primary minerals are mandatory for the management of the vineyard soils in the Colli Albani and, in general, it is significative for the vineyards in volcanic areas.