The luminescence of [SnCl3]- in acetonitile (τ=1.6 μs) is quenched by oxygen with k=3.8×108 L mol-1 s-1.This quenching is associated with an electron transfer from [SnCl3] n in its 3P1 sp-excited state to O2. Secondary processes lead to the formation of SnOCl2(CH3CN)n, with an overall quantum yield of φ=1.5 at λirr=2.54 nm. While this Sn(IV) complex is not light sensitive, [SnCl6]2- in CH3CN undergoes a photochemical reductive elimination with the generation of [SnCl3]- with φ=0.015 at λirr=2.54 nm