Vitrification technology is a promising method for hardless and resourceful treatment of hazardous waste. However, the vitrification of high-Fe hazardous waste ash is difficult due to its high-Fe content, which can lead to the crystallization or phase separation of glass. In this paper, based on the composition of high-Fe hazardous waste ash, 385 glass formulations with SiO2-Al2O3-CaO-Na2O-TiO2-Fe2O3 systems were designed using extreme vertices design method. Optical microscopy, X-ray diffraction and acid dissolution test were employed to identify 136 formulations to form glass samples exhibiting excellent chemical durability. Based on CART model analysis, the study determines the range of glass formulation for high-Fe hazardous waste ash with optimal glass-forming ability, in mass fraction (w): 40.0%≤w(SiO2)≤55.0%, 10.0%≤w(CaO)<14.0%, 14.0%≤w(Na2O)≤18.0%, 5.0%≤w(Other)<9.5% or 35.0%≤w(SiO2)<40.0%, 9.0%≤w(TiO2)≤10.0%, 5.0%≤w(Other)<9.5%. The research in this paper provides design and computation for glass vitrification of high-Fe hazardous waste ash.