2-Butanone (methyl ethyl ketone) is a high-octane next-generation biofuel candidate synthesized through microbiological pathways from biomass. The flame structure and species formed in 2-butanone combustion are of interest when further considering this compound for use as a fuel. Thus species profiles within a fuel-rich laminar premixed flat flame of 2-butanone were measured. Two experiments which used different facilities and measurement techniques were combined i.e. the first using electron ionization molecular-beam mass spectrometry (MBMS) and the second relied on synchrotron-generated vacuum UV photoionization MBMS. Very good agreement between both measurements was obtained. The experiments identified the formation of a number of toxic oxygenated intermediates such as methyl vinyl ketone (MVK) acetaldehyde and formaldehyde. 2- Butanone showed the lowest overall concentrations for species that could contribute to potentially hazardous volatile emissions underlining its attraction as a fuel also from this perspective.