In　the　present　work,　we　report　a　facile　oxalate-derived　hydrothermal　method　to　fabricate　α-,　β-　and　δ-MnO2　catalysts　with　hierarchically　porous　structure　and　study　the　phase-dependent　behavior　for　selective　oxidation　of　H2S　over　MnO2　catalysts.　It　was　disclosed　that　the　oxygen　vacancy,　reducibility　and　acid　property　of　MnO2　are　essentially　determined　by　the　crystalline　phase.　Systematic　experiments　demonstrate　that　δ-MnO2　is　superior　in　active　oxygen　species,　activation　energy　and　H2S　adsorption　capacity　among　the　prepared　catalysts.　As　a　consequence,　δ-MnO2　nanosphere　with　a　hierarchically　porous　structure　shows　high　activity　and　stability　with　almost　100%　H2S　conversion　and　sulfur　selectivity　at　210　°C,　better　than　majority　of　reported　Mn-based　materials.　Meanwhile,　hierarchically　porous　structure　of　δ-MnO2　nanosphere　alleviates　the　generation　of　by-product　SO2　and　sulfate,　promoting　the　adoptability　of　Mn-based　catalysts　in　industrial　applications.　©　2021　Elsevier　B.V.