The　intrinsic　acceptor-rich　ZnO　(A-ZnO)　microtubes　fabricated　by　optical　vaporization　supersaturated　precipitation　(OVSP)　are　compatible　to　microfluidic　channel　for　on-chip　photodegradation.　Unfortunately,　the　micron　size　and　weak　charge　separation　ability　in　bare　A-ZnO　microtube　limit　its　degradation　rate.　Design　of　heterojunction　structure　is　a　feasible　way　to　improve　the　photocatalytic　performance　by　efficient　separation　of　photogenerated　carriers.　Here　we　synthesize　p-CuO　and　n-ZnS　nanostructures　on　A-ZnO　microtubes,　respectively,　achieving　various　hierarchical　heterojunctions.　The　massive　Zn-vacancy-related　shallow　acceptor　carries　in　A-ZnO　as　well　as　the　similar　bandgap　and　crystal　structure　of　A-ZnO/n-ZnS　achieve　the　highest　photodegradation　efficiency　up　to　0.105　min(-1).　It　is　about　twice　and　triple　higher　than　bare　A-ZnO　microtubes　and　n-ZnO　nanoparticles,　respectively.　The　formed　type　II　heterojunction　in　A-ZnO/n-ZnS　boosts　the　charge　separation　superior　to　other　ZnO-based　heterojunction.　The　present　work　paves　a　new　way　to　the　tubular　A-ZnO-based　hierarchical　heterojunction　with　n-type　wide-bandgap　semiconductors　for　high-performance　optoelectronic　devices.