Borosilicate glasses are the primary waste forms for the industrial immobilization of high‐level liquid waste. Yet, the compositional variation of waste glasses can form the diopside phase, which can be detrimental to the melting process and the properties of the final glass products. This study prepared simulated waste glasses with variable contents of alkaline earth metals, boron, transition metals, and rare earth metal oxide and subjected them to heat treatments. The effect of the compositional variation on the diopside crystallization behavior was explored using differential scanning calorimetry, X‐ray diffraction, optical microscopy, and scanning electron microscopy‐energy dispersive spectroscopy. The results revealed that the average size of diopside crystals was proportional to the square root of the heat treatment durations. Increased contents of alkaline earth and transition metal oxides could contribute to the growth of diopside crystals, while boron oxide tended to inhibit it. Finally, a prediction model correlating the average crystal size, compositional variation, and heat treatment durations was discussed.