Hierarchical-pore　Pd@Co3O4,　Pd@Co3O4/C,　and　Pd@Co/CNT　(CNT　=　carbon　nanotube)　were　fabricated　via　the　one-step　pyrolysis　of　palladium@zeolitic-imidazolate-framework-67　(Pd@ZIF-67);　these　catalysts　employed　as　heterogeneous　catalysts　displayed　excellent　performance　in　the　Heck　reaction.　These　Pd@ZIF-67　derivatives　retain　the　skeleton　of　the　precursor　and　provide　abundant　exposed　Pd　active　sites,　and　the　pyrolysis　treatment　creates　rich　hierarchical　pores　affording　a　convenient　path　for　reaction　substrates　accessing　the　active　sites.　As　a　result,　they　exhibit　significantly　enhanced　yields　(＞99%)　in　the　Heck　reaction　of　iodobenzene　with　styrene,　compared　with　that　of　Pd@ZIF-67　(78%).　In　addition,　these　catalysts　can　be　easily　recovered　by　magnetic　separation　and　reused　without　losing　activity.　The　Pd@Co/CNT　was　also　used　in　catalyzing　other　Heck　reactions,　showing　good　performance.　The　work　thus　indicates　a　feasible　method　in　the　construction　of　hierarchical-pore　catalysts　from　treating　metal@MOF　(metal-organic　framework)　composites　for　various　organic　reactions.