We　report　herein　a　facile　pyrolysis　etching　strategy　for　the　fabrication　of　UiO-66-xs　single　crystals　with　tunable　coordination　unsaturated　zirconium　sites　(Zr-CUS)　as　well　as　interconnected　mesoporosity.　The　synthesis　is　realized　by　having　pristine　UiO-66-xs　subjected　to　thermal　treatment,　which　results　in　the　selective　decompo-sition　of　thermal-sensitive　organic　linkers　and　hence　the　creation　of　permanent　mesoporosity,　leaving　abundant　Zr-CUS　with　enhanced　degree　of　exposure.　The　prepared　hierarchically　porous　UiO-66-xs　(HP-UiO-66-xs)　were　innovatively　applied　for　mild　oxidation　of　H2S　into　polysulphur,　achieving　near　100　%　H2S　conversion　and　polysulphur　selectivity　in　a　wide　range　of　temperatures.　The　superior　activities　can　be　well　maintained　in　a　continuous　test　of　over　50　h.　The　Zr-CUS　of　HP-UiO-66-xs　effectively　activate　H2S　and　O2　via　the　＂adsorption　dissociation　tandem　hydrogen　transfer＂　mechanism,　and　the　abundant　mesochannels　ensure　efficient　transport　of　reactants　and　bulky　products　in　and　out　HP-UiO-66-xs,　leading　to　catalytic　activities　superior　to　those　of　traditional　H2S　selective　oxidation　catalysts.