Dimethyl ether appears to be a better choice among various diesel alternatives due to its high cetane number and sootless combustion. However, the physical and chemical properties of dimethyl ether are very different from those of diesel. The physical properties influence spray formation and atomization characteristics, while chemical properties determine combustion and emission formation characteristics. Thus, fuel's physical and chemical properties significantly determine engine performance and emissions. In the present work, spray combustion and emission formation characteristics of n-heptane, dimethyl ether, and their blends (10, 25, and 50% dimethyl ether in n-heptane) were numerically studied in a constant volume chamber. Results show that the n-heptane spray combustion has the highest heat release rate with an intense premix combustion phase, whereas dimethyl ether spray combustion has the lowest heat release rate and shortest premix combustion phase. The magnitude of the premixed phase and heat release rate decreases with the increase in dimethyl ether mass fraction in the blends. Soot, carbon monoxide (CO), unburned hydrocarbon (UHC), and nitric oxide (NO) emissions decreased with the increase in the dimethyl ether mass fraction in the blends and were lowest for the dimethyl ether.