Rare earth based luminescent materials have emerged as a focal point of the scientific investigation owing to their remarkable optical behaviour and potential applications. An effort has been made to develop a series of Ce3+ doped CaWO4 nano-phosphors using an ethylene-glycol assisted reflux route. The detailed structural and morphological properties have been examined through various analytical techniques. The +3-oxidation state of the activator ion Ce has been verified through the XPS study. The change in optical band gap due to the substitution is well discussed using diffuse reflectance spectroscopy. In Photoluminescence study, a broad emission centred at 465 nm is observed due to the 5D3/2→2FJ transitions (J = 7/2 and 5/2) and a significant enhancement in the emission peak is obtained for the optimized phosphor. Concentration quenching phenomenon, observed after 3 mol% of Ce3+ is mainly mediated by the electric multipole-multipole type interaction. The CIE diagram indicates the tuning of emission colour from blue to white region and the emission near white region for the optimized phosphor is further authenticated by its low colour purity value (43 %). The effective tunability of photo-physical properties and colorimetric parameters suggest the applicability of the optimized nano-phosphor in solid state lighting especially for outdoor illumination.