In this study, the viscometer was used to evaluate the viscosity of slag containing 10%SiO2 with varying CaO/Al2O3 ratios. When CaO/Al2O3 ratio increased in the 3.00 to 4.00 range, the viscosity exhibited a non‐monotonic behavior characterized by an initial decrease followed by an increase, with a minimum value of 0.046 Pa·s observed at 1673 K. The slag with a CaO/Al2O3 ratio above 3.00 had relatively low and stable viscosity within the range of 1373 K to 1673 K, which was beneficial for slab quality of high‐aluminum steel. X‐ray diffraction and Raman spectroscopy were used to better understand the viscosity evolution of slag containing 10%SiO2. A higher CaO/Al2O3 ratio depolymerized network structures due to the breaking effect of free oxygen O2‐. Upon surpassing a CaO/Al2O3 ratio of 3.50, the transformation of the crystallization phase occurs from CaO·SiO2 to 2CaO·SiO2. Additionally, a higher CaO/Al2O3 ratio promoted the precipitation of the 11CaO·7Al2O3·CaF2 crystal in the slag.This article is protected by copyright. All rights reserved.