The ultrathin K2O·nSiO2 based laminated anti-fire glass with super-multilayer morphology is prepared by a gradient heating method using a high SiO2 content (55 wt%) and low viscosity (684.5mPa.s ± 43.8mPa.s, 48 rpm) SiO2 core-shell emulsion. Meanwhile, K2O·nSiO2 with uniform morphology as a comparison sample is prepared by a thermostatic method using the same SiO2 emulsion. This article systemically characterized and analyzed the viscosity, morphology, hardness, ultraviolet (UV), and fire-resistant performance. The mechanism of shear-thinning characteristics is obtained by monitoring the viscosities of these SiO2 core-shell emulsions. The super-multilayer and uniform morphology are shown in SEM micrographs, and the UV-resistant capacity is more than 3000 h for outdoor use. Still, the hardness of the former is more than the latter. The foaming expansion layer has ensured window integrity under the fire. This work has provided a new simple routine for preparing ultrathin K2O·nSiO2 based laminated anti-fire glass for architectural safety applications.