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To detect an air-fuel ratio in wide range is very important to control the automotive engines with low fuel consumption and low exhaust emissions. Although the application of zirconia electrolyte for this purpose has been proposed by the authors several years ago, there remained several problems due to the contamination of gas diffusion apertures which are exposed to the exhaust gas environment. Here the behavior of ions transported in zirconia electrolyte have been analyzed to optimize the structure and characteristics, and to guarantee the long life operation of sensor. Gas contents and their reactions in combustion process under the wide range air-fuel ratio have been analyzed, and these results were reflected to the analysis of ion transportation in zirconia electrolyte. Experimental results supported the analytical results, and they showed the possibilities of long life operation of zirconia air-fuel ratio sensor utilizing ion transportation phenomena.