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From the point of global and local environment, internal combustion engine is facing the need for significant improvement of exhaust emission. Especially, important is the reduction of unburned hydrocarbon (HC) from fuel film on liner under cold condition. In this study, at first, quantitative fuel film measurement technique by using Laser Induced Exciplex Fluorescence (LIEF) was developed. For the light source, 4th harmonic pulse yttrium aluminum garnet (YAG) laser (266nm) was used. For the tracer, the combination of N,N-Dimethylaniline (DMA) and naphthalene was used and quantitative concentration was decided by calibration test. With LIEF, the distribution of fuel film can be obtained by measuring the fluorescence only from the liquid phase. In order to evaluate the effect of fuel film on exhaust HC emission from engine, the film distribution was measured using quartz glass liner. For the injector, a prototype 6-hole gasoline injector was used.