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In this paper, we communicate a new type of Auger-free luminescence (AFL) compounds, alkali tin fluorides ASnF3 (A = Na, K, Rb and Cs). The luminescence in these compounds originates due to the electron transition from the top valence band (VB) of tin- orbital to the outermost core levels of halogen, i.e., halogen- orbital (- transitions). The AFL of these compounds is expected to be of L-type. Furthermore, the electronic band structures and optical properties such as dielectric functions, refractive index and energy loss function are also investigated using ab initio calculations. [ABSTRACT FROM AUTHOR]