Abstract　Gold　nanoparticles　loaded　on　the　special　three-dimensional　urchin-like　micro/nano　hierarchical　TiO2　microspheres,　with　CuO　layer　modification,　are　performed　for　the　CO　preferential　oxidation　in　H2-rich　stream　at　room　temperature　under　visible　light　irradiation　or　not.　It　is　found　that　the　suitable　outer　decoration　of　CuO　in　TiO2　microspheres　can　obviously　improve　the　catalytic　activity　of　Au/TiO2,　and　adding　visible　light　can　further　promote　the　performance.　Based　on　the　characterizations　of　catalysts,　it　is　proposed　that　the　CuO　layer　distributed　on　the　shell　of　TiO2　urchin-like　microspheres　can　enhance　the　electron　transfer　among　Au,　TiO2　and　CuO　sites　to　drive　the　increase　in　surface　electron　densities　of　Au　and　support　sites　induced　by　both　the　localized　surface　plasmon　resonance　of　Au　nanoparticles　and　the　photo-excitation　of　CuO　under　visible　light　irradiation,　resulting　in　the　adsorptions　and　activations　of　CO　and　O2.　Therefore,　as　a　synactic　result　of　its　unique　band　gap　relation,　its　unique　electron　property　and　its　morphologic　effect,　the　novel　CuO　modified　TiO2　support　not　only　enhances　the　microstrain　itself　on　the　stabilization　of　the　size　of　Au　nanoparticles,　but　more　importantly　also　reinforces　the　electron　interaction　between　support　and　Au　sites.　©　2015　Elsevier　B.V.　All　rights　reserved.