Fe-doped　LaCoO3　perovskite　catalysts　synthesized　via　a　facile　citric　acid-assisted　sol-gel　route　have　been　applied　for　the　H2S　selective　oxidation.　The　as-synthesized　LaFexCo1−xO3　perovskites　exhibit　a　randomly　macroporous　structure　formed　by　the　accumulation　of　nanoparticles.　Characterization　studies　reveal　that　appropriate　Fe　substitution　effectively　enhances　the　formation　of　oxygen　vacancies,　and　thus　improves　the　lattice　oxygen　mobility　and　H2S　adsorbability,　respectively.　The　obtained　LaFe0.4Co0.6O3　exhibited　remarkable　catalytic　activity,　with　the　H2S　conversion　and　sulfur　yield　of　100%　at　190　°C.　A　combined　approach　of　in-situ　FT-IR　and　in-situ　Raman　experiments　disclosed　that　the　plausible　reaction　pathway　of　H2S　selective　oxidation　over　LaFexCo1−xO3　perovskites　follows　the　Mars-van　Krevelen　mechanism.　The　density　functional　theory　calculations　revealed　that　Fe-doping　improves　the　formation　of　oxygen　vacancy　and　enhances　the　adsorption　of　H2S.　This　study　offers　new　insights　for　the　design　of　highly　efficient　perovskites　for　the　selective　oxidation　of　H2S.　©　2023　Elsevier　B.V.