The　method　to　construct　the　three-dimensional　(3D)　ordered　nanostructure　of　ZnO　for　improving　its　performance　has　attracted　considerable　attention　and　remains　a　challenging　issue,　which　has　theoretical　and　practical　implications　for　nanoscale　applications　such　as　optoelectronics　and　gas　sensors.　Herein,　we　demonstrate　a　straightforward　chemical　vapor　deposition　(CVD)　technique　for　the　epitaxial　growth　of　3D　cross-linked　comb-like　ZnO　arrays　on　r-plane　sapphire　substrates.　The　morphological,　structural,　and　optical　properties　of　the　as-synthesized　samples　were　examined　using　X-ray　diffraction,　field　emission　scanning　electron　microscopy,　field　emission　transmission　electron　microscopy,　Raman　spectroscopy,　UV-vis　spectroscopy,　and　photoluminescence　spectroscopy.　A　cooperative　growth　mechanism　is　suggested　to　construct　3D　cross-linked　comb-like　ZnO　arrays:　The　supersaturated　alloy　forms　a　backbone　of　oblique　nanosails　along　[101̅0]　by　the　Au-assisted　catalytic　vapor-liquid-solid　(VLS)　growth　mechanism　and　the　inevitable　vapor-solid　(VS)　lateral　extension　growth　process;　simultaneously　discrete　nanoteeth　are　grown　along　the　unilateral　c-direction　[0001]　by　the　Zn　self-catalytic　VLS　mechanism,　culminating　in　a　3D　cross-linked　array　of　comb-like　ZnO.　The　development　of　such　a　unique　3D　cross-linked　array　allows　the　exploration　of　performance　in　gas-sensitive　devices,　optoelectronics,　and　quantum　electrical　information　applications.　©　2023　American　Chemical　Society.