The study presents data on the role of lithological factors in the divergence of soil formation in forest–steppe and steppe ecosystems in a region of the East European Plain characterized by extremely contrasting geogenic conditions. Soils from different lithologic–geomorphologic combinations in the Samara region were chosen as the study object. It was shown that, in some cases, bioclimatogenic conditions are less decisive in the formation of the morphological organization and basic chemical parameters of the solum than the lithological characteristics of a particular locality. These lithological factors can transform soil morphology and affect the taxonomic position of soils at the subtype level and below. In landscapes marked by spatial and lithological contrasts at meso- and macro-levels, the use of a bioclimatic classification approach becomes inadequate, because it fails to highlight individual soil features. Thus, the development of lithological taxonomic and diagnostic criteria is necessary for the protection, proper use, and mapping of soils in complex geogenic, particularly lithological, conditions. Within one soil climatic zone, there can exist a large number of lithological soil subtypes, genera, and varieties. In such cases, the lithological framework has a stronger influence on soil spatial distribution than climatic gradients and associated vegetation ecotones.