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With increasing interest in new biofuel candidates, 1-octanol and di-n-butylether (DNBE) were presented in recent studies. Although these molecular species are isomers, their properties are substantially different. In contrast to DNBE, 1-octanol is almost a gasoline-type fuel in terms of its auto-ignition quality. Thus, there are problems associated with engine start-up for neat 1-octanol. In order to find a suitable glow-plug position, mixture formation is studied in the cylinder under almost idle operating conditions in the present work. This is conducted by planar laser-induced fluorescence in a high-speed direct-injection optical diesel engine. The investigated C8-oxygenates are also significantly different in terms of their evaporation characteristics. Thus, in-cylinder mixture formation of these two species is compared in this work, allowing conclusions on combustion behavior and exhaust emissions.