The present investigation deals with the effect of calcination temperature on the structural and thermoluminescent (TL) properties of Zn2SiO4 materials. For this study, Zn2SiO4 was prepared via a simple hydrothermal route and calcinated at temperatures from 700°C to 1100°C in an air atmosphere. TL data of all Zn2SiO4 samples showed two peaks at around 240°C and 330°C due to the formation of the luminescence centre during X‐ray irradiation. More interestingly, the Zn2SiO4 sample calcinated at 900°C exhibited a shift in the TL peak (282°C and 354°C) with an optimal TL intensity attributed to its good crystallinity with a well‐defined hexagonal plate‐like morphology. X‐ray‐irradiated Zn2SiO4 samples calcinated at 900°C exhibited a high‐temperature TL glow curve peak, suggesting that the present material could be used for high‐temperature dosimetry applications.