Abstract Dual-fuelling in compression–ignition (CI) engines is a mode of combustion where a small pilot injection of high-cetane fuel (i.e. diesel) ignites a premixed high-octane fuel (i.e. methane) and air mixture. This allows conventional CI engines to lower their emissions of smoke and nitrogen oxides ( NO x ) while maintaining their high thermal efficiencies. However, poor ignitability of the main fuel–air charge results in increased emissions of unburnt hydrocarbons (HC) and carbon monoxide (CO). Conventional pilot fuels such as diesel and biodiesel (methyl esters transesterified from raw plant oil) have been researched extensively in prior work, showing that in terms of performance and emissions they perform fairly similarly. This is because the physical, chemical and combustion properties of various methyl esters are comparable to those of conventional diesel. In order to reduce these emissions of HC and CO, alternative pilot fuels need to be considered. As fuels employed during normal CI engine operation, both dimethyl ether (DME, a gaseous CI engine fuel) and water-in-fuel emulsions (conventional biodiesel mixed with varying concentrations of water) have shown that they reduce smoke and NO x emissions significantly, while improving combustion quality. In this work, the performance of DME and water-in-biodiesel emulsions as pilot fuels was assessed. It was seen that the water-in-biodiesel emulsions did not perform as well as expected, as increased HC and CO emissions coupled with a mild change in NO x levels was encountered (compared to conventional pilot fuel, in this case neat biodiesel). The emulsions performed very poorly as pilot fuels below a certain BMEP threshold. DME, while producing higher levels of HC and CO than neat biodiesel, managed to reduce NO x significantly compared to neat biodiesel. Emissions of HC and CO, while higher than neat biodiesel, were not as high as levels seen with the emulsions. Thermal efficiency levels were generally maintained with the liquid pilot fuels, with the DME pilot producing comparatively lower levels.