A　novel　alumina　nanowire　(ANW)　solid-phase　microextraction　(SPME)　fiber　coating　was　prepared　by　a　simple　and　rapid　anodization-chemical　etching　method　for　ultra-selective　determination　of　volatile　esters　and　alcohols　from　complicated　food　samples.　Preparation　conditions　for　ANW　SPME　fiber　coating　including　corrosion　solution　concentration　and　corrosion　time　were　optimized　in　detail　for　better　surface　morphology　and　higher　surface　area　based　on　scanning　electron　microscope　(SEM).　Under　the　optimum　conditions,　homogeneous　alumina　nanowire　structure　of　ANW　SPME　fiber　coating　was　achieved　with　the　average　thickness　of　20.　μm　around.　Compared　with　most　of　commercial　SPME　fiber　coatings,　ANW　SPME　fiber　coatings　achieved　the　higher　extraction　capacity　and　special　selectivity　for　volatile　esters　and　alcohols.　Finally,　an　efficient　gas　sampling　technique　based　on　ANW　SPME　fiber　coating　as　the　core　was　established　and　successfully　applied　for　the　ultra-selective　determination　of　trace　volatile　esters　and　alcohols　from　complicated　banana　and　fermented　glutinous　rice　samples　coupled　with　gas　chromatography/mass　spectrometry　(GC/MS)　detection.　It　was　interesting　that　25　esters　and　2　alcohols　among　30　banana　volatile　organic　compounds　(VOCs)　identified　and　4　esters　and　7　alcohols　among　13　identified　VOCs　of　fermented　glutinous　rice　were　selectively　sampled　by　ANW　SPME　fiber　coatings.　Furthermore,　new　analytical　methods　for　the　determination　of　some　typical　volatile　esters　and　alcohols　from　banana　and　fermented　glutinous　rice　samples　at　specific　storage　or　brewing　phases　were　developed　and　validated.　Good　recoveries　for　banana　and　fermented　glutinous　rice　samples　were　achieved　in　range　of　108-115%　with　relative　standard　deviations　(RSDs)　of　2.6-6.7%　and　80.0-91.8%　with　RSDs　of　0.3-1.3%　(n=3),　respectively.　This　work　proposed　a　novel　and　efficient　gas　sampling　technique　of　ANW　SPME　which　was　quite　suitable　for　ultra-selectively　sampling　trace　volatile　esters　and　alcohols　from　complicated　food　samples.　©　2013　Elsevier　B.V.