In the east of the Tuvinian trough within the Kropotkin Ridge, the formation of Devonian volcanic associations was intimately conjugate with rifting on the southwestern framing of the Siberian Platform. The associations include picrite-like basalts, trachybasalts, basaltic trachyandesites, trachyandesites, trachytes, trachyrhyodacites, trachyrhyolites, comendites, and subvolcanic dolerites. The basic and normal-basic rocks are subdivided into two groups by TiO2 contents: high-Ti (TiO2 ∼ 2.2–4.2 wt.%) and medium-Ti (TiO2 ∼ 1.3–2.0 wt.%). Compared with the high-Ti basites, the medium-Ti ones are depleted in K, Rb, REE, Nb, Ta, Th, and U and have features of magmatic series of active continental margins. The high-Ti rocks are similar in composition to within-plate basalts. But in the isotopic compositions of Sr and Nd the above groups of basites are similar and correspond to mantle sources forming enriched within-plate basalts of the OIB type. This combination of within-plate and continent-marginal geochemical features in the basites localized in the same structure-geologic conditions might indicate the formation of rock associations in the rift zone at the rear of active continental paleomargin during the evolution of their common plume source. Its interaction with the suprasubductional lithospheric mantle determined the geochemistry of rocks.