ABSTRACT In this work, NaGdF4: 20%Yb, 2%Er microcrystals with varying contents of Cr3+ doping were obtained by conventional hydrothermal process. The microcrystal phase structure, morphology, upconversion luminescence mechanism, as well as temperature sensing behaviour under different treatment methods were researched. Based on the thermally coupled 2H11/2 and 4S3/2 levels of Er3+ and the dependence of fluorescence intensity ratio (FIR) on temperature, the optical temperature sensing behaviour of micrometer crystals were experimentally demonstrated. The NaGdF4: 20%Yb, 2%Er, 7%Cr microcrystals treated with high-temperature annealing show the best temperature sensing behaviour within the temperature span of 298–498 K. NaGdF4: 20%Yb, 2%Er, 7%Cr microcrystals with high temperature annealing presented the feasibility and promising properties for optical temperature sensing. The endeavour of emerging materials could lay the groundwork for future sustainable photonics engineering industrial growth.