Successfully　designed　and　synthesized　PS@Ni@Cu　core–shell　composite　microspheres,　which　provide　efficient　electronic　transmission　for　anisotropic　conductive　films　for　electronic　packaging　applications.　Herein,　a　simple　method　for　preparing　core–shell　composite　microspheres　using　Pickering　emulsion　polymerization　as　a　template,　a　dense　nano-nickel　shell　layer　was　coated　on　the　surface　of　polystyrene　to　obtain　PS@Ni　microspheres,　the　microspheres　have　conductivity　and　magnetic　properties.　Then　the　microspheres　were　coated　with　nano-copper　layer　by　electroless　plating　to　enhance　the　mobility　of　electrons　in　specific　media.　Finally,　the　microspheres　are　laminated　in　epoxy　resin,　which　can　realize　directional　(horizontal,　inclined,　and　vertical)　movement　under　magnetic　field　force　to　form　anisotropic　conductive　film.　The　conductivity　is　171.68　S　cm−1,　the　adhesiveness　and　conductivity　of　the　film　can　be　changed　by　adjusting　the　content　of　microspheres.　The　film　has　excellent　thermal　stability,　good　adhesion,　and　can　be　anisotropic　conductive.　The　difference　in　conductivity　between　the　conductive　direction　and　the　insulating　direction　is　about　108　orders　of　magnitude,　and　it　can　adapt　to　strong　acids　and　alkalis　and　other　more　extreme　environments.　It　is　significance　to　the　development　of　electronic　packaging　and　is　expected　to　be　widely　used　in　the　field　of　electronic　devices.　©　2022　John　Wiley　&　Sons　Ltd.