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Conventional near-infrared luminescent phosphors activated by transition metal elements or rare earth activators were already widely reported. In this work, we develop a self-activated near-infrared luminescent phosphor with a typical double perovskite structure, which exhibits an emission at 650–750 nm under excitation at 365 nm. The origin of the desired luminescence in (Ca,Sr)LaMgTaO 6 compounds is attributed to the oxygen vacancies defects, oxygen interstitial defects and substitution defects and antioccupation defects. Thermal quenching of photoluminescence is undesirable with an integrated emission loss of 30–50% at 150 °C, which needs to be improved. This new series of near-infrared luminescent materials have potential applications in agricultural cultivations and bio-imaging materials. More importantly, we demonstrate a strategy by self-activation to realize near-infrared light. [ABSTRACT FROM AUTHOR]