Tholeiitic basalts and trachytes of the bimodal association of Wangtian’e volcano are studied. It is shown that trachytes formed with the leading role of crystal fractionation of the parental tholeiitic magma. It has been identified from the melt inclusion study that hedenbergite and plagioclase phenocrysts of trachytes from Wangtian'e volcanic neck crystallized in the temperature range of 1080–1100 and 1050–1060°C, respectively. After heating experiments with melt inclusions in plagioclase of trachytes, in some cases relics of carbonates and CO2 were observed in the inclusions. The trachyte phenocrysts host water-bearing Fe-rich globules and CO2 inclusions with carbonate phases. The Fe-rich silicate globules are often intergrown with titanomagnetite and are covered by amorphous carbon films. A model is suggested explaining the formation of water-bearing Fe-rich globules and CO2 inclusions with carbonate relics as a result of silicate–silicate and silicate–carbonate liquid immiscibility, that was caused by the evolution of the parental basaltic melt. Upon the trachytic melt ascending to the surface, the ferrocarbonate liquid was decomposed on magnetite, carbon, and carbon dioxide.