This work considers micas present both as phenocrysts in granular xenoliths and as large xenocrysts in the phreatomag-matic deposits, which characterize the final volcanic activity of Colli Albani volcanic complex, Roman Comagmatic Region (central Italy). In these micas the Fe/(Fe+Mg) ratio spans from 0.06 to 0.55, thus the micas range from phlogopite to magnesian annite through ferroan phlogopite. Heterovalent octahedral substitutions involve Ti, Al and also Cr but in very limited amounts. In the interlayer, Ba for K substitution occurs up to 0.06 apfu. Crystal structure refinements were determined in space groups C2/m and C2/c for the 1M and 2M1 polytypes, respectively (agreement factor, Robs: 0.021 ≤ Robs ≤ 0.035). The crystal structure of these micas is greatly affected by the annitic substitution. An increase in the annitic component is reflected by a decrease in distortion affecting both individual tetrahedra (tetrahedral angle variance, TAV: 0.49 ≤ TAV ≤ 1.13°2) and the entire tetrahedral ring [6.6 ≤ α ≤ 10.34°]. The interlayer topology is affected as well. A strong correlation exists between Fe and Ti; thus, the same correlations found for Fe apply to Ti also. Another strong correlation exists between heterovalent octahedral substitutions and the (OH)- site deprotonation. In contrast, heterovalent interlayer substitutions are accompanied by substitution of F- for (OH)-. Despite their scattered occurrence in pyroclastics, these micas nicely represent the overall crystal chemical trends of micas, which re-crystallized undisturbed in magma before this reached explosive conditions. One crystal of the dataset considered may represent a phenocryst in a hypabissal body disrupted by one of the many explosive phases of the Alban Hills volcanism.