Dimethyl ether (DME) and n-pentanol can be derived from non-food based biomass feedstock without unsettling food supplies and thus attract increasing attention as promising alternative fuels, yet some of their unique fuel properties different from diesel may significantly affect engine operation and thus limit their direct usage in diesel engines. In this study, the influence of n-pentanol, DME and diesel blends on the combustion performance and emission characteristics of a diesel engine under low-temperature combustion (LTC) mode was evaluated at various engine loads (0.2–0.8 MPa BMEP) and two Exhaust Gas Recirculation (EGR) levels (15% and 30%). Three test blends were prepared by adding different proportions of DME and n-pentanol in baseline diesel and termed as D85DM15, D65P35, and D60DM20P20 respectively. The results showed that particulate matter (PM) mass and size-resolved PM number concentration were lower for D85DM15 and D65P35 and the least for D60DM20P20 compared with neat diesel. D60DM20P20 turned out to generate the lowest NOx emissions among the test blends at high engine load, and it further reduced by approximately 56% and 32% at low and medium loads respectively. It was found that the combination of medium EGR (15%) level and D60DM20P20 blend could generate the lowest NOx and PM emissions among the tested oxygenated blends with a slight decrease in engine performance. THC and CO emissions were higher for oxygenated blends than baseline diesel and the addition of EGR further exacerbated these gaseous emissions. This study demonstrated a great potential of n-pentanol, DME and diesel (D60DM20P20) blend in compression ignition engines with optimum combustion and emission characteristics under low temperature combustion mode, yet long term durability and commercial viability have not been considered.