Abstract: The correlation between the impact toughness and microstructural characteristics of a large bainitic steel bloom has been investigated. The study focuses on microcrack nucleation and propagation in the basic cleavage plane. To analyze the phase transformation during the wind-cooling process, the temperature field of the bloom was acquired by computer simulation, and a continuous cooling transformation experiment was conducted. The results show that compared with the surface of the bloom, the toughness of the bloom’s core is decreased by the increase in proeutectoid ferrite and the coarsening of tempered martensite–austenite constituents. The proeutectoid ferrite decreases the toughness via its effects on carbide precipitation, the formation of martensite–austenite constituents, and the bainite transformation. The relatively large tempered martensite–austenite constituents are conducive to microcrack nucleation and propagation.