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Porous anodic aluminum oxide (AAO) templates were prepared by a two-step anodization process, then chemical vapor deposition (CVD) method was used to prepare well-aligned open-ended multiwall carbon nanotube (MWCNT) arrays in the AAO templates that also served as catalyst. Gas ionization sensors were fabricated using the MWCNT arrays. The gas ionization sensors featured the electrical breakdown of the ethanol vapor of different concentrations at the carbon nanotube tips, the breakdown voltage decreased with the increase of the ethanol quantity. They had showed good sensitivity and repeatability for detecting ethanol vapor of low concentration in the test gas.