The present study aimed to investigate the influence of the gradual substitution of Fe2O3 by Al2O3 on the thermal properties of polyphosphate glasses. The conducted considerations based on differential scanning calorimetry (DSC) and heating microscopy thermal analysis provided much essential information about the correlation between glass chemical composition and its characteristic parameters, such as transformation temperature, specific heat, crystallization temperature, crystallization enthalpy, the activation energy of crystal growth, melting temperature, and Angell glass thermal stability. The obtained estimation of viscosity changes as a function of temperature could be very helpful for researchers to correctly plan the vitrification process and thus radioactive waste immobilization. A precise analysis of DSC curves and X-ray diffraction patterns revealed the possibility of crystallization process design in order to create materials with different levels of crystallinity and phase composition. The drawn conclusions allow choosing the glass with the optimal concentration of Al2O3 and Fe2O3, which ensures the relatively low melting temperature, viscosity, and glass crystallization ability, with application potential in nuclear waste immobilization.