The high-temperature syngas and molten slag droplets discharged from entrained-flow coal gasifiers contain a large amount of heat energy, which can be efficiently recovered by radiant syngas coolers (RSCs). However, it is hard to know the solidification degree of molten slag droplets at the outlet of an RSC during industrial operations. In this work, the industrial-scale RSC and molten slag droplet models are established to predict the solidification degree of slag droplets at the outlet of the RSC. Then, the effects of slag diameter, syngas flow field, slag initial temperature, slag porosity, and slag pore structure are investigated by numerical simulations, and residence time as well as complete solidification time are calculated by coupling of a discrete-phase model and a solidification model. The results indicate that as the slag droplet diameter increases, the residence time of the slag droplet shortens, but the complete solidification time increases. When the slag droplet diameter is greater than or equal to 3.0 mm, the complete solidification time is larger than the residence time, and the slag droplet cannot solidify completely at the outlet of the RSC. The solidification degree in the windward zone is greater than that in the leeward zone. Although the slag initial temperature has little effect on the solidification, a lower slag initial temperature is still conducive to a greater solidification degree. Additionally, the pore structure facilitates solidification, and the promoting effect of penetrated pores is more remarkable than that of closed pores. A larger porosity is also beneficial to accelerate the solidification of molten slag droplets and increase the solidification degree.