The　development　of　efficient　catalysts　is　of　great　significance　in　the　photocatalytic　ozonation　process　for　organic　wastewater　treatment.　However,　the　effect　of　exposed　facets　and　surface　defects　of　the　catalyst　on　the　photocatalytic　ozonation　performance　is　less　covered.　Herein,　ZnO　nanocomposites　with　different　preferentially　exposed　crystal　facets　(ZnO-rod　and　ZnO-disk)　were　synthesized　and　used　for　photocatalytic　ozonation　of　phenol.　The　characterization　and　density　functional　theory　calculation　results　demonstrated　that　the　exposed　{0001}　facets　and　oxygen　vacancies　promoted　the　separation　and　transfer　of　photogenerated　charges　as　well　as　improved　the　adsorption　and　activation　of　ozone　molecules　on　the　catalyst　surface.　Consequently,　the　TOC　removal　rate　in　the　UV-O3/ZnO-disk　process　(62.4%)　was　much　higher　than　those　in　the　UV-O3/ZnO-rod　process　(41.3%)　and　the　UV-O3　process　(15%).　Moreover,　the　experimental　results　of　the　identification　and　quenching　of　active　species　illustrated　that　˙OH　was　more　likely　to　be　produced　in　the　UV-O3/ZnO-disk　process,　while　1O2　was　more　likely　to　be　formed　over　ZnO-rod.　A　large　amount　of　˙OH　with　a　stronger　oxidation　capability　than　1O2　contributed　to　the　superiority　of　ZnO-disk　over　ZnO-rod　in　organic　pollutant　removal.　This　work　demonstrates　that　the　engineering　of　crystal　facets　and　surface　defects　provides　an　effective　strategy　for　constructing　efficient　catalysts　for　the　photocatalytic　ozonation　process.　©　2023　The　Royal　Society　of　Chemistry.