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In present era, rare earth doped nanophosphors are the key architecture in the development of white light-emitting diodes (WLEDs) and their performance has become a major topic of interest among the researchers. Still, the deficiency of orange phosphor has become a barrier for the commercialization of the WLED. In this work, single phase intense orange light emitting Na+ co-activated CaTiO3 (CTO):Sm3+ nanophosphor is synthesized via modified sol–gel method with an average particle size of 60 nm. The synthesized nanophosphor strongly exhibits bright orange emission under 408 nm excitation. Comparative photoluminescence (PL) analysis of CTO:Sm3+ and Na+ co-doped CTO:Sm3+ nanophosphors irrefutably reveals that incorporation of Na+ facilitates almost threefold increase in the luminescence intensity along with significant improvement in thermal stability. Obtained results conclusively suggest that strong orange emitting Na+ co-activated Sm3+ doped CTO nanophosphor could be a potential candidate for use in blue light chip based warm WLED and others lighting device applications. [ABSTRACT FROM AUTHOR]