The ability of premixed low-temperature diesel combustion to deliver low particulate matter (PM) and NOx emissions is dependent on achieving optimal combustion phasing. Small deviations in combustion phasing can shift the combustion to less optimal modes, yielding increased emissions, increased noise, and poor stability. This paper demonstrates how variations in fuel cetane number affect the detailed combustion behaviour of a direct-injection, diesel-fuelled, premixed combustion mode. Testing was conducted under light load conditions on a modern single-cylinder engine, fuelled with a range of ultra-low sulphur fuels with cetane numbers ranging from 42 to 53. Fuel cetane number is found to affect ignition delay and, accordingly, combustion phasing. Gaseous emissions are a function of combustion phasing and exhaust gas recirculation (EGR) quantity, but are not directly tied to fuel cetane number. Fuel cetane number is merely one of many different engine parameters that shift combustion phasing. Furthermore, the operating range is constrained by the changes in cetane number: no injection timings yield acceptable combustion across the whole spread of tested cetane numbers. However, in terms of combustion phasing, the operating range is consistent, independent of fuel cetane number.