Dual-fuel premixed charge compression ignition (DF-PCCI) combustion has been demonstrated as a promising solution for simultaneous reduction of nitrogen oxides (NOx) and particulate matter (PM) emissions in heavy-duty compression ignition engines. The use of natural gas (NG) as the low-reactivity fuel in DF-PCCI combustion can expand the limited range of high load operations owing to the lower reactivity of NG than that of gasoline. However, the lower reactivity of NG results in significant hydrocarbon (HC) and carbon monoxide (CO) emissions at the low load operations. In this study, the mixture formations with and without exhaust gas recirculation (EGR) in NG-diesel DF-PCCI combustion were assessed to reduce the HC and CO emissions as well as to improve the fuel economy at low load operations. Diesel injection timing and NG substitution ratio (SR), which is defined as the proportion of energy stored in NG with respect to the total energy amount, were changed to examine the effects of the mixture formation on the DF-PCCI combustion. The NG SR, which was required to maintain the combustion phasing at a constant crank angle degree (CAD), was increased as the diesel injection timing was retarded in the mixture formation without EGR. The introduction of EGR, in addition to the diesel injection timing and the NG SR, contributed to the favorable mixture formation for the low load operations. The NOx and PM emissions were lower than the EURO VI limitations in both the mixture formations with and without EGR. When the EGR rate of 50% was applied, the indicated thermal efficiency (ITE) increased compared to the case without EGR. The increased ITE was due to the improved combustion efficiency, the higher peak heat release rate (HRR), and the shorter combustion duration. The HC and CO emissions also decreased significantly with the EGR.