Volcanic clasts from the International Ocean Discovery Program Site U1431 in the South China Sea (SCS) were analyzed for V isotopic compositions in this study. These volcanic clasts represent mantle-derived carbonated melts and record the transition from carbonated melts to alkali basalts. Based on the formation sequence, these clast samples were divided into early-stage (> 8.3 Ma) and late-stage (< 8.3 Ma) clasts. The early-stage volcanic clasts have δ51V values of −0.76‰ to −0.67‰, which provide an estimate for the V isotopic composition of primary carbonated melts. Their V isotopic compositions are slightly heavier than those of mid-ocean ridge basalts (−0.84‰ ± 0.10‰) and bulk silicate Earth (−0.86‰ to −0.91‰), reflecting the control of low-degree partial melting under conditions of high oxygen fugacity. The late-stage volcanic clasts have δ51V values ranging from −0.62‰ to 0.29‰, which are systematically heavier than those of early-stage volcanic clasts. The carbonated melts rose through and reacted with the lithospheric mantle and were transformed into alkali basalts by dissolving orthopyroxene and precipitating olivine and/or clinopyroxene. Because the reactants and reaction products do not lead to significant V isotope fractionation, the V isotopes show limited variations during transformation from carbonated melts to alkali basalts. The alkali basalts were emplaced into shallow crust by multiple pulses, in which the magma experienced variable degrees of magma differentiation, with δ51V values close to those of the initial alkali basalts or increasing due to fractional crystallization of FeTi oxides. The change in V isotopic compositions from early-stage volcanic clasts to late-stage volcanic clasts was driven by the varying magnitude of influence exerted by different magmatic processes en route from the deep mantle to the shallow crust.