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The purpose of this study was to characterize the air/fuel ratio (AFR) of turbulent premixed flames in a spark-ignition (SI) engine. We developed a spark plug sensor with an optical fiber to detect the chemiluminescence spectra, specifically the intensity of the spectral lines related to OH*, CH*, and C2* free radicals. The sensor was composed of a sapphire window and optical fiber and is applicable to automobile SI engines. Measurements of the chemiluminescence intensity from OH*, CH*, and C2* radicals were obtained in turbulent premixed flames with a propane-air mixture for different AFRs in a compression-expansion machine (CEM). The performance of the spark plug sensor was compared with a Cassegrain reflector using an intensified charge-coupled device. The results showed good agreement with measurements obtained using the Cassegrain reflector. The spark plug sensor was shown to be useful for measuring chemiluminescence of turbulent premixed flames in an SI engine.