Zircon is a promising candidate for use as a matrix in the immobilization of radioactive waste. However, high temperatures (1400–1600 °C) and calcination durations are generally required to produce it. In this letter, we report the synthesis of cerium-containing solid solution based on zircon Zr1-xCexSiO4 by means of a straightforward and environmentally sustainable milling-assisted solid-phase approach conducted at a reduced temperature. Our study demonstrated that the utilization of mechanical activation of the oxide mixture in a mill not only diminished the temperature (to 1200 °C) and the duration of calcination but also increased the Ce content in zircon up to 6.4 at.%. Additionally, we propose a novel method for determining the phase composition of calcined samples using Vegard's law and mass balance.