Selective　oxidation　of　H2S　is　a　satisfactory　alternative　to　traditional　Claus　process　for　H2S　removal.　A　facile　template-free　strategy　was　developed　to　controllably　synthesize　MgAl2O4　with　different　Mg/Al　molar　ratios　for　this　application.　It　is　deduced　that　the　rich-Al　spinel　structure　can　accommodate　a　large　number　of　Mg　vacancies　(V-Mg　＇＇),　and　adjacent　unsaturated　coordination　lattice　oxygen　could　be　converted　into　oxygen　vacancies　(V-O(center　dot　center　dot)).　Moreover,　porous　flake-like　structure　was　successfully　fabricated.　The　distinctive　structure　endows　the　catalyst　with　satisfactory　mass　transmission　channels　and　high　approachability.　As　a　result,　the　optimal　sample　with　the　highest　content　of　V-Mg　＇＇　exhibits　favorable　desulfurization　performance,　ca.　100　%　H2S　conversion　and　100　%　S　yield　at　180　degrees　C,　which　is　better　than　most　of　reported　metal-oxide　desulfurizers.　The　chemically　adsorbed　oxygen　and　V-Mg　＇＇　play　decisive　roles　in　this　process.　Furthermore,　the　property　of　catalytic　sites　and　plausible　reactivity　route　for　the　H2S-selective　oxidation　over　MgAl2O4　are　presented,　which　supply　a　feasible　motive　impetus　for　the　design　of　efficient　sulfur　removal　catalysts.