The precipitation, growth, and transformation of carbides rich in Cr and Mo during solidification and cooling process of high‐alloy steel for cold working dies are investigated. The Fe–C pseudobinary phase diagram of high‐alloy steel is calculated by Thermo‐Calc software to ascertain the critical phase transformation temperatures. The temperatures of phase transformation during the solidification process are determined by a differential scanning calorimeter. Then the microstructure of the samples at these characteristic temperatures is observed in situ by high‐temperature confocal microscope. The results show that the characteristic temperatures for phase transformation and carbide precipitation are 1380, 1315, 1140, and 980 °C, respectively. At 1315 °C, thick rod‐like or island‐like M7C3 carbides enriched in Cr and Fe are formed. At 1140 °C, secondary M7C3, adhering to the primary eutectic M7C3, grows rapidly in a rod‐like morphology and maintains a similar composition. The secondary M6C carbides of segregated Mo elements precipitate in fan‐shaped clusters near M7C3 through the dissolution of M7C3 and the conversion of M2C. Thermodynamic calculation further indicates that the eutectic Cr7C3 precipitates at 1213 °C, and secondary Cr7C3 remains under conditions favorable for precipitation below the solidus, preceding the precipitation of secondary carbides Cr23C6 and Mo2C.