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The objective of this study was to reduce pollutant emissions during cold start conditions in a spark-ignited direct injection engine, by exploring the potential of oxygenated fuels. With their high oxygen content and lack of direct C-C bonds, they effectively reduce particle number (PN) and NOx emissions under normal conditions. Methanol was chosen due to its wide availability. As methanol is toxic to humans and associated with cold-start issues, a second promising synthetic fuel was selected to be benchmarked against gasoline, comprising 65 vol% of dimethyl carbonate and 35 vol% of methyl formate (C65F5). Currently, there is a lack of detailed investigations on the cold start performance for both oxygenated fuels utilizing today’s injector capabilities. Spray measurements were caried out in a constant volume chamber to assess the spray of C65F35. Reduced fuel temperature increased spray-penetration length and compromised fast vaporization.