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Emissions of Unburned Hydrocarbons (UHC) from diesel engines are a particular concern during the starting process, when after-treatment devices are typically below optimal operating temperatures. Drivability in the subsequent warm-up phase is also impaired by large cyclic fluctuations in mean effective pressure (MEP). This paper discusses in-cylinder wall temperature influence on unburned hydrocarbon emissions and combustion stability during the starting and warm-up process in an optical engine. A laser-induced phosphorescence technique is used for quantitative measurements of in-cylinder wall temperatures just prior to start of injection (SOI), which are correlated to engine out UHC emission mole fractions and combustion phasing during starting sequences over a range of charge densities, at a fixed fueling rate. Squish zone cylinder wall temperature shows significant influence on engine out UHC emissions during the warm-up process.