Considering non-equilibrium solidification and its influence on subsequent near-equilibrium solidification together, the description of recalescence behavior in bulk undercooled Cu70Ni30 alloy was adopted to predict the corresponding microstructure transition. The thermal plateau time for near-equilibrium solidification can be deduced directly with the calculation of non-equilibrium solid fraction formed in recalescence. On the basis of quantitative description for recalescence behavior, the non-equilibrium solid fraction, residual liquid fraction, dendrite broken-up time, and thermal plateau time can be determined as functions of initial undercooling. Then, a simple and accurate application of dendrite fragmentation model was performed as the grain refinement at both low- and high-undercooling originates from dendrite breakup. The predicted undercooling regions for the double grain refinement agree well with the experimental observation. Moreover, the change of grain morphology for the second grain refinement can be ascribed to the occurrence of recrystallization produced by the enhanced residual stress upon highly undercooled solidification.