Co-combustion performance of blends of municipal solid waste with high ash content and low calorific value and corn stalk was investigated using a thermogravimetric analyzer coupled with a Fourier transform infrared spectroscopy. Ignition temperature, emissions of major gaseous pollutants, and the ash characterization were studied. The ashes of the blends were characterized with Fourier transform infrared, X-ray diffraction, and a nitrogen adsorption analyzer. The results show that SO2 and NO emission from the blends are a little higher than that from municipal solid waste. X-ray diffraction results indicate that the reaction between calcium in corn stalk and chlorine to form CaCl2 results in an HCl reduction from co-combustion. The higher surface area and pore volume of ash shows that the blends undergo complete combustion.