In the future, synthetic fuels could replace fossil fuels to minimize the CO2 emissions of combustion engines. Dimethyl carbonate (DMC) and methyl formate (MeFo) represent not only possible synthetic fuels but, due to their oxygen content, also have properties to reduce the pollutant emissions. For a good combustion process, the spray targeting and evaporation properties are important. Due to the less known injection behavior of DMC and MeFo, the spray characteristics were examined in a pressure chamber. The penetration depth, projected spray area, and spray angle were investigated at injection pressures of 100 and 200 bar, chamber pressures of 1 and 2.5 bar, and a temperature variation of up to 90°C for two different injector spray angles and flow rates in comparison with gasoline E5. The spray was recorded with a high-speed camera in a constant-volume chamber with a N2 environment. Both fuels showed a faster evaporation than E5 even with a higher injection mass due to their lower LHV. MeFo showed extreme spray collapse and flash boiling effects, which lead to even faster evaporation rates and higher penetration velocities.