In　the　study,　nanoporous　array　anodic　alumina　(NAAA)　prepared　by　a　simple,　rapid　and　stable　two-step　anodic　oxidization　method　was　introduced　as　a　novel　solid-phase　microextraction　(SPME)　fiber　coating.　The　regular　nanoporous　array　structure　and　chemical　composition　of　NAAA　SPME　fiber　coating　was　characterized　and　validated　by　scanning　electron　microscopy　and　energy　dispersive　spectroscopy,　respectively.　Compared　with　the　commercial　polydimethylsiloxane　(PDMS)　SPME　fiber　coating,　NAAA　SPME　fiber　coating　achieved　the　higher　enrichment　capability　(1.7-4.7　folds)　for　the　mixed　standards　of　volatile　organic　compounds　(VOCs).　The　selectivity　for　volatile　alcohols　by　NAAA　SPME　fiber　coating　demonstrated　an　increasing　trend　with　the　increasing　polarity　of　alcohols　caused　by　the　gradually　shortening　carbon　chains　from　1-undecanol　to　1-heptanol　or　the　isomerization　of　carbon　chains　of　some　typical　volatile　alcohols　including　2-ethyl　hexanol,　1-octanol,　2-phenylethanol,　1-phenylethanol,　5-undecanol,　2-undecanol　and　1-undecanol.　Finally,　NAAA　SPME　fiber　coating　was　originally　applied　for　the　analysis　of　biological　VOCs　of　Bailan　flower,　stinkbug　and　orange　peel　samples　coupled　with　gas　chromatography-mass　spectrometry　(GC-MS)　detection.　Thirty,　twenty-seven　and　forty-four　VOCs　of　Bailan　flower,　stinkbug　and　orange　peel　samples　were　sampled　and　identified,　respectively.　Moreover,　the　contents　of　trace　1-octanol　and　nonanal　of　real　orange　peel　samples　were　quantified　for　the　further　method　validation　with　satisfactory　recoveries　of　106.5　and　120.5%,　respectively.　This　work　proposed　a　sensitive,　rapid,　reliable　and　convenient　analytical　method　for　the　potential　study　of　trace　and　small　molecular　biological　VOCs　by　the　novel　NAAA　SPME　fiber　coating.　©　2012　Elsevier　B.V.