Multilayer　graphene　reinforced　copper　matrix　(Cu-MLG)　composites　were　fabricated　via　molecular-level　mixing　combined　with　vacuum　hot-pressing　(VHP).　The　MLG　displayed　a　preferred　orientation　in　the　copper　matrix,　with　the　in-plane　surface　perpendicular　to　the　hot-pressing　direction,　resulting　in　significant　anisotropy　in　the　thermal　properties　of　Cu-MLG　composites.　Theoretical　predictions　were　made　using　four　models　(Schapery,　Kerner,　Turner　and　mixture　rule)　to　investigate　the　effect　of　the　preferential　orientation　of　MLG　on　the　CTE　anisotropy　of　Cu-MLG　composites.　The　CTE　anisotropy　was　further　analyzed　by　carrying　out　molecular　dynamics　(MD)　simulations　to　determine　the　variation　in　bond　lengths　for　copper　and　MLG　in　different　directions　in　the　interface　regions.　The　MLG　bond　length　increased　gradually　with　increasing　temperatures　in　the　in-plane　direction,　while　in　the　out-plane　directions,　it　increased　significantly　at　first　and　then　decreased　at　higher　temperatures.　The　variations　of　bond　lengths　for　MLG　are　consistent　with　the　CTE　anisotropy　of　the　Cu-MLG　composites　in　the　same　direction.　(C)　2018　Elsevier　B.V.　All　rights　reserved.