Inner vapor pressure and temperature of vulnerable explosive spalling positions in refractory castables during rapid drying were measured by embedding pressure transmitting pipes and thermocouples during casting. The measured vapor pressure, temperature, and tensile strength of the castables were analyzed and discussed. A hollow sphere shell model was used to analyze the stress induced by the vapor pressure based on the structure of refractory castables. The mechanism of refractory castables explosive spalling caused by vapor-induced pore split was proposed. By comparing the vapor-induced stress and the tensile strength of the castables, the explosive spalling mechanism was validated quantitatively.