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Phosphor thermometry was used during fuel injection in an optical engine with the glass piston of reentrant type. SiO2 coated phosphor particle was used for the gas-phase temperature measurements, which gave much less background signal. The measurements were performed in motored mode, in combustion mode with injection of n-heptane and in non-combustion mode with injection of iso-octane. In the beginning of injection period, the mean temperature of each injection cases was lower than that of the motored case, and temperature of iso-octane injection cases was even lower than that of n-heptane injection cases. This indicates, even if vaporization effect seemed to be the same at both injection cases, the effect of temperature decrease changed due to the chemical reaction effect for the n-heptane cases. Chemical reaction seems to be initiated outside of the fuel liquid spray and the position was moving towards the fuel rich area as the time proceeds.