Slag regulation is crucial for achieving smelting of high-alumina iron ore in blast furnaces. This study investigated the fluidity and structure of CaO-SiO2-10 wt.%MgO-30 wt.%Al2O3 slag by varying the CaO/SiO2 ratio (1.0-2.0). The results revealed that viscosity decreased with increasing CaO/SiO2 ratio, while the free running temperature, defined as the temperature at which the slag can flow freely, initially increased and then decreased, peaking at the range of 1.2-1.6. Interestingly, the free running temperature of slag at basicity 2.0 (1392 degrees C) was lower than that at basicity 1.0 (1398 degrees C). Spectroscopic analysis demonstrated that increasing basicity facilitated greater charge compensation of Al3+ ions, resulting in an increased amount of [AlO4] tetrahedra. Moreover, increasing free oxygen promoted the depolymerization of [SiO4] and [AlO4] tetrahedra, reducing bridging oxygen and increasing non-bridging oxygen. Consequently, the slag's overall polymerization degree decreased. Furthermore, MD simulations identified two distinct fracture mechanisms of bridging oxygen within the Si-O-Si structure.