An　iodine-functionalized　metal–organic　framework　(MOF),　UiO-68-I,　was　synthesized.　UiO-68-I　showed　good　catalytic　activity　for　dibromination　of　alkenes　and　alkynes　with　a　low　catalyst　loading　of　1%　and　was　able　to　be　recycled　and　recovered　efficiently.　Mechanistic　studies　suggest　that　UiO-68-I　may　trigger　the　formation　of　molecular　bromine　through　a　radical　intermediate　and　thus　accelerate　the　reaction.　The　activity　and　stability　of　UiO-68-I　outperforms　most　earlier　reports　on　organoiodine　catalysts,　showing　the　great　potential　of　iodine-functionalized　MOFs　as　recyclable　heterogeneous　hypervalent　iodine　reagents　or　catalysts.　©　2022　Elsevier　B.V.