Er3+ activated Sr3WO6 double perovskite crystallized in triclinic structure was synthesized via the solid-state reaction method at 1200 °C for non-contact optical thermometry and solid-state lighting. The phosphors under study were characterized via X-ray diffraction, scanning electron microscopy, diffusion reflectance spectra, and photoluminescence techniques. When excited with 380 nm, the Sr3WO6:Er3+ phosphors exhibited intense green emission, corresponds to 2H11/2/4S3/2-4I15/2 transitions of Er3+. The fluorescence intensity ratio of thermally coupled energy levels were computed within 303–513 K and subsequent relative sensitivity (0.56% K−1 at 303 K) was determined. Moreover, the PL intensity maintained 76.28% at LED burning temperature (150 °C) compared to PL intensity observed at room-temperature, denotes good thermal stability. Additionally, the fluorescent behaviour of the phosphors was examined via PL decay lifetime study. The PL quantum efficiency of the phosphor is computed via the Auzel's model using PL decay lifetime, and was obtained to be 80.32% for Sr3WO6:2% Er3+ phosphor.