The impact of coal fly ash (FA) is often ignored in the co-utilization of biomass and coal. Therefore, the influence of FA on the properties of pyrolysis products made from corn straw (CS) was investigated in this study. First, the distribution of co-pyrolysis bio-oil was investigated using pyrolysis-gas chromatography and mass spectrometry at 500°C-800 °C. Then, in a free-falling fixed-bed reactor, FA and CS were co-pyrolyzed, gaseous product yields were computed, and solid product composition and morphology were determined using X-ray diffraction, scanning electron microscopy, and the N2 adsorption–desorption isotherm, respectively. According to the findings, FA greatly promoted the degradation of oxygen-containing components in bio-oil and the formation of aromatic compounds at higher temperatures. The CS5-FA1 was the most favorable ratio for bio-oil production at 800 °C. Furthermore, the addition of FA had the highest stimulating effect on CO2 at 500 °C and 800 °C, and the yield of the other pyrolysis gases (CH4, CO, and H2) was also increased at 800 °C.