Using fly ash as the modifier, blast furnace slag was modified to prepare slag wool, fulfilling the goal of using one type of waste to make use of another type of waste, and it is of great significance for the comprehensive utilization of industrial bulk solid wastes and resource recycling. In the process of forming fiber from blast furnace slag, fluidity is the key factor affecting the smooth formation of fiber from slag. To explore the changes in the fluidity of modified blast furnace slag, the temperature-dependent viscosity of modified blast furnace slag with different amounts of fly ash added was measured, and the effects of fly ash addition on the viscosity, fluidity, and activation energy of particle migration, and slag structure of modified blast furnace slag were investigated. The results indicated that with the increase in the amount of fly ash added, in the high-temperature region (>1324 °C), the viscosity of modified blast furnace slag increases gradually, the fluidity decreases gradually (i.e., the fluidity becomes worse), and the suitable fiber-forming temperature range gradually widens. When the fly ash addition increases from 5% to 25%, the trend of the activation energy of slag particle migration is as follows: increase, decrease, increase significantly, decrease. When the addition of fly ash is less than 20%, the SiO2 content and slag temperature jointly affect the breakage and reorganization of oxygen bridge bonding in the silicon-oxygen tetrahedron in the slag structure. When the addition of fly ash increases to 25%, the slag temperature dominates the breakage of oxygen bridge bonding in the silicon-oxygen tetrahedron in the slag structure. When using fly ash as the modifier to prepare slag wool, from the perspective of slag fluidity and process operability, the optimum addition amount of fly ash is 15%.