The heat transfer model for steel solidification in Al2O3 crucial and permanent mold by finite element method was developed and validated by temperature measurement. The multi-gradient operation was novelly designed, and the tailored cooling rate in range of 0.1–10 °C/s was obtained at the target location. The simulation aided experiment with the large-sized samples was carried out, and the local cooling rate was verified by secondary dendrite arm spacing. The size of austenite grain decreases slightly as cooling rate increases from 0.15 °C/s to 0.31 °C/s, and then increases dramatically in the range of 0.31–0.48 °C/s, finally decreases with cooling rate increasing further to 9.76 °C/s. The relationship between austenite grain size and cooling rate was logarithmically regressed in the range of 0.48–9.76 °C/s, in which the kinetic equations on basis of cooling experiment and continuously cast slab can also work. However, the grain size decrease in 0.15–0.31 °C/s and then increase in 0.31–0.48 °C/s cannot be described. Based on the mechanism of peritectic solidification, the austenite grain growth is mainly controlled by diffusion at a low cooling rate smaller than 0.31 °C/s, and the final grain size is less than 1.0 mm. At a medium cooling rate between 0.48 and 3.60 °C/s, austenite grain growth is accelerated by the energy stored during massive type peritectic transformation previously, and the grain size is between 1.7 and 2.9 mm. At high cooling rate larger than 9.76 °C/s, austenite grains grow to about 0.9 mm in columnar shape. The time for grain growth is not adequate, although addition energy storage by massive transformation can also occur. The critical cooling rate for the onset of massive type peritectic transformation in the large-sized sample is between 0.31 and 0.48 °C/s. The growth velocity in the isothermal experiment is much smaller than that in continuous cooling process, confirming that the austenite grain evolution is significantly affected by previous peritectic solidification.