The article is devoted to the petrogeochemical features of Neogene collision volcanism in the central part of the Lesser Caucasus within Azerbaijan. The main goal of the study is to determine the thermodynamic conditions for the formation of Neogene volcanism in the central part of the Lesser Caucasus using the available petrogeochemical material. Using factor analysis, as well as the “IGPET”, “MINPET”, “Petrolog-3” programs, material balance calculations were performed that simulate the phenocryst fractionation process, the crystallization temperature, pressure, and figurative nature of the rock-forming minerals of the formation rocks were calculated. It was determined that at the early and middle stages of crystallization of the rocks of the andesite-dacite-rhyolite formation, the fractionation of amphibole played an important role in the formation of subsequent differentiates. Based on computer simulation, it was revealed that rocks of the andesite-dacite-rhyolite formation were formed by fractional crystallization of the initial high-alumina basaltic magma of high alkalinity in the intermediate magma foci. The calculations of the balance of the substance, simulating the process of fractionation of phenocrysts, as well as magnetite, confirmed the possibility of obtaining rock compositions from andesites to rhyolites as a result of this process. In this case, the process of crystallization differentiation was accompanied by processes of contamination, hybridism and mixing. Based on the geochemical features of rare and rare-earth elements, changes in their ratios, the nature of the mantle source and the type of fractionation process are determined. It was revealed that the enrichment of formation rocks by light rare earths, as well as by many incoherent elements, is associated with the evolution of enriched mantle material. Under high water pressure, as a result of the fractionation of olivine and pyroxene, high-alumina basalts are formed from primary high-magnesian magma, which can be considered parental magma. It was established that, in contrast to the elevated Transcaucasian zone in the more lowered East Caucasus, under conditions of increased fluid pressure and reduced temperature, the melt underwent fractional crystallization in the intermediate centers, being enriched with alkaline, large-ion lithophilic elements, light REEs, etc. This is evidenced by the presence of large crystals of feldspars, the contamination of these minerals by numerous crystals of biotite, magnetite, several generations of these minerals, zonality, as well as the presence of related “water” inclusions, such as hornblendites, hornblende gabbro, etc. The physicochemical conditions for the formation of Neogene volcanic rocks of the Lesser Caucasus are determined.