Two Canadian tar sands derived experimental diesel fuels with cetane numbers of 26 and 36 and a reference fuel with a cetane number of 47 were tested in a Deutz (F1L511D), single cylinder, A stroke, naturally aspirated research engine. The fuels were tested at intake and cooling air temperatures of 30 and 0°C. The 36 cetane number fuel was tested with advanced, rated and retarded injection timings. Poor engine speed stability at light loads and excessive rates of combustion pressure rise were experienced with the lowest cetane number fuel. Detailed performance/combustion behavior is presented and a correlation with fuel structural composition is made. The analytical techniques used to characterize the fuels included liquid chromatography, gas chromatography mass spectrometry (GC-MS) and proton nuclear magnetic resonance spectrometry (PNMR).