Basic oxygen furnace (BOF) steel slag is a main by-product produced during the converter steelmaking process. The volume instability and fast crystallization property of the BOF slag limit its added-value application. The present study investigates the effect of Al2O3 addition on the microstructure modification and crystallization kinetics of a high basicity BOF steel slag. Continuous cooling transformation (CCT) and time-temperature-transformation (TTT) curves have been constructed using a confocal scanning laser microscopy (CSLM) to determine the relation between cooling rate and behavior of the crystallization process. The critical cooling rate to vitrify the slags was experimentally obtained. The crystallization sequence has been clarified by integrating the in-situ and post-mortem observations with thermodynamic calculation. This article provides a fundamental understanding on the effect of Al2O3 on mineralogical and morphological modification, aiming to improve the hydration potential of the high basicity BOF steel slag.