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Laser-induced exciplex fluorescence has been applied to the mixture formation process in the combustion chamber of an optically-accessible four-cylinder in-line spark-ignition engine in order to distinguish between liquid and vapor fuel distribution during the intake and compression stroke for different injection timings. The naphthalene/N,N,N′N′-tetramethyl p-phenylene diamine (TMPD) exciplex system excited at 308nm with a broadband XeCl excimer laser is used to obtain spectrally-separated, single-shot fluorescence images of the liquid or vapor phase of the fuel. For different timings of the fuel injector this technique is applied to obtain crank-angle-resolved images of the resulting mixture in the combustion chamber. The fluorescence light is detected with an intensified slow-scan CCD-camera equipped with appropriate filters.