A　major　challenge　in　utilizing　metal–organic　frameworks　(MOFs)　for　volatile　organic　compound　(VOC)　capture　was　their　inclination　for　strong　adsorption,　which　consequently　impeded　desorption　and　elevated　energy　demand.　To　overcome　this　challenge,　the　construction　of　HKUST-1@Cu　nanofibers　(HK@Cu-NF)　with　thermal　conductive　adsorption　sites　was　proposed　to　synchronous　enhance　toluene　adsorption　and　desorption　efficiency　for　VOCs　capture.　In　this　work,　Cu-based　HKUST-1　was　designed　to　grow　on　Cu　nanofibers,　and　formed　uniform　coverage　MOF　layer　with　tight　connection　via　homologous　Cu　self-transformation　growth　strategy.　The　synthesized　composite　was　proved　to　maintain　high　surface　area　(1473　m2/g)　and　generate　abundant　unsaturated　Cu　sites　on　its　nanointerface　based　from　the　thermally　conductive　Cu　nanofibers.　This　unique　connection　structure　endowed　these　adsorption　sites　with　high　affinity　towards　toluene　and　high　thermal　conductivity　as　well,　and　finally　formed　thermal　conductive　adsorption　sites.　As　a　result,　HK@Cu-NF　composite　(80　%　loading　of　HKUST-1)　exhibited　1.9　times　higher　of　toluene　adsorption　capacity　at　P/P0　=　0.002　and　＞3　times　higher　of　thermal　diffusivity　than　pure　HKUST-1.　Furthermore,　it　achieved　enhancement　in　both　adsorption　and　desorption　efficiency　for　toluene,　which　reached　4.8　and　6.9　times　of　pure　HKUST-1.　Therefore,　construction　of　thermal　conductive　adsorption　sites　successfully　improved　the　adsorption　efficiency　and　regeneration　efficiency　for　VOCs　capture,　and　realized　the　low　energy　VOCs　desorption　process.　©　2024　Elsevier　B.V.