An experimental investigation is conducted on the influence of EGR (Exhaust Gas Recirculation) rates (0–40%) on the combustion and emission characteristics of n-butanol/diesel/PODE3-4 blends at low-temperature combustion mode in diesel engine. The results show that at identical EGR rate, compared to D100 (diesel fuel), the peak values both of the mean cylinder pressure and the heat release rate of BD20 (20% butanol and 80% diesel in volume) are increased, ignition delay is extended, and the brake thermal efficiency is enhanced. Concerning BD20 blended with PODE3-4, the ignition delay is shortened, while both the brake thermal efficiency and the combustion efficiency increase. At the EGR rate below 30%, as the EGR rate grows, the effects on emission of soot, CO and HC are not significant, while the emission of NOx is sharply reduced; when the EGR rate is above 30%, as it grows, the emissions of soot, CO, and HC drastically rise. As EGR rate grows, the total particulate matter (PM) number concentrations of four fuels firstly decline and then rise, the total PM mass concentrations keep stable firstly and then rise drastically. As the proportion of added PODE3-4 in BD20 grows, the particle geometric mean diameters further decrease.