Gas　response　control　through　structural　and　defect　engineering　in　metal　oxides　are　critical　approaches　to　realize　high　performance　sensors.　Herein,　we　present　the　fabrication　of　ZnO　thin　films　containing　nanosized　structures　and　high　concentration　of　zinc　interstitials　for　NO2　and　ethanol　monitoring.　The　target　materials　were　fabricated　by　aerosol　assisted　chemical　vapour　deposition　(AACVD)　method　on　ceramic　and　glass　substrates,　and　were　characterized　by　complementary　analytical　techniques.　The　obtained　ZnO　nanoparticulate　and　nanopyramidal　thin　films　yielded　an　outstanding　response　of　similar　to　41　to　1　ppm　NO2　and　similar　to　236　towards　100　ppm　ethanol,　respectively.　The　reasons　accounting　for　such　an　enhancement　were　revealed　by　the　surface-depletion　model　in　ZnO　and　the　chemisorption　energies　of　oxygen　molecules　on　Zn-i-enriched　crystal　facets.