The oldest igneous rocks in the Paleoproterozoic (~1.88–1.85 Ga) North Baikal postcollisional volcanoplutonic belt of the Siberian craton are the basaltoids of the Malaya Kosa Formation (Akitkan Group). The youngest are the composite (dolerite–rhyolite) and doleritic dikes cutting the granitoids of the Irel’ complex and the felsic volcanic rocks of the Khibelen Formation (Akitkan Group). The position of Malaya Kosa basaltoids in the Akitkan Group section and published geochronological data on the felsic volcanic rocks overlying Malaya Kosa rocks suggest that their age is ~1878 Ma. The rhyolites from the center of a composite dike were dated by the U–Pb zircon method at 1844 ± 11 Ma, and the dolerites in the dikes are assumed to be coeval with them. Malaya Kosa basaltoids correspond to high-Mg tholeiites and calc-alkaline andesites, whereas the dolerites in the dikes correspond to high-Fe tholeiites. Geochemically, these basaltoids and dolerites are both similar and different. As compared with the dolerites, the basaltoids are poorer in TiO2 (an average of 0.89 vs. 1.94 wt.%), (9.54 vs. 14.71 wt.%), and P2O5 (0.25 vs. 0.41 wt.%). However, these rocks are both poor in Nb but rich in Th and LREE, εNd(T) being negative. According to petrographic and geochemical data, they derived from compositionally different sources. It is assumed that the basaltoids originated from subduction-enriched lithospheric mantle, whereas the dolerites originated from refractory lithospheric mantle metasomatized by subduction fluids. The isotopic and geochemical features of mafic rocks in the North Baikal belt are well explained by their formation during crustal extension which followed subduction and collision in the region. The early stages of postcollisional extension evidenced the melting of subduction-enriched lithospheric mantle with the formation of parent melts for Malaya Kosa basaltoids. At the final stages of the formation of the North Baikal belt, during the maximum crustal extension, Fe-enriched melts rose to the surface and generated the dolerites of the dikes.