We describe the stratigraphy, chronology, and grain size characteristics of the white trachytic tuff (WTT) of Roccamonfina Volcano (Italy). The pyroclastic rock was emplaced between 317 and 230 Ma BP during seven major eruptive events (units A to G) and three minor events (units BC, CD, and DE). These units are separated by paleosol layers and compositionally well-differentiated pyroclastic successions. Stratigraphic control is favored by the occurrence at the base of major units of marker layers. Four WTT units (1 to 4) occur within the central caldera. These are not positively correlated with specific extracaldera units. The source of most of the WTT units was the central caldera. Units B and C were controlled by the western wall of the caldera, whereas units D and E were able to overcome this barrier, spreading symmetrically along the flanks of MC. The maximum pumice size (MP) of units increases with distance from the caldera, whereas the maximum lithic size (ML) decreases. MP and ML of the marker layer of unit D (MKDa–MKDp) do not show any systematic variations with respect to the central caldera. In contrast, the thickness of surge MKDa decreases with distance from the source, and MKDp accumulates to the north of MC probably controlled, respectively, by mobility-transport power and by wind blowing northwards. The grain size characteristics of the WTT deposits are used for classifying the units. There is no systematic variation of the grain size as a function of stratigraphic height either among units or within single units. Large variation of components in subunit E1, with repetitive alternation of pyroclastic flow to surge through fallout vs. surge deposits, suggests that the process of eruption took place in a complex or piecemeal fashion. Pumice concentration zones (PCZ) occur at all WTT levels on the volcano, but they are much thicker and pumice clasts are much larger within the central caldera. These were probably originated by the disruption of lava (flow or dome) to pumice fragments and fine ash due to sudden depressurization and interaction with lake waters of the molten lava. Local basal PCZ are, in some cases, similar to the lapilli-rich “layer 1P” that has been described elsewhere, and may have been deposited from currents transitional between pyroclastic surge and flow. Other basal PCZ formed in response to small undulations in the substrate, or can be originated by fallout. Lenticular PCZ within ignimbrite interiors and tops are interpreted to record marginal pumice levees and pumice rafts, some of which were buried by subsequant pyroclastic flows. Lithic concentration zones (LCZ) also occur at various stratigraphic height within the extracaldera ignimbrites, whereas intracaldera LCZ are absent, probably due to the fact that ignimbrite currents are strongly energetic and erosive near vent. LCZ at the top of basal inversely graded layers are formed by mechanical sieving or dispersive pressure in response to variable velocity gradients and particle concentration gradients (a segregation process). Coarse LCZ and coarse lithic breccias (LB), that reside in the interior or tops of pyroclastic flows and that occur in medial to distal areas, are interpreted to be the result of slugs of lithic-rich debris introduced by vent collapse or rockslides into the moving pyroclastic flows along their flow paths. These LCZ become mixed to varying degrees due to differential densities and velocities relative to the pyroclastic flows (desegregation processes).