This paper describes the effect of the ash content in biomass on the distribution of pyrolysis products and the miscibility of bio-oil in diesel. Ash content of loblolly pine wood (0.5 wt %, 1.1 wt %, and 1.5 wt %) was systematically varied by impregnating the wood with potassium carbonate solution. Variation in the ash content did not create a significant change in the chemical composition of the impregnated biomass. However, the response to a variety of thermal treatments changed significantly. The volatile matter content decreased from 88.3% to 78.2%, while the bio-oil yield declined from 45.7% to 29.9% as the ash content increased. Although the total organic yield decreased with increased biomass ash content, the total concentration of phenolic monomers increased from 2.8 mg/g to 20.2 mg/g, and bio-oil miscibility with a commercial diesel fuel increased from 6.7% to 13.4% based on wet bio-oil. The miscibility of guaiacol and 4-methyl guaiacol in diesel was higher than that of catechol, due to the lower polar and hydrogen bonding contribution. Test in a diesel engine showed a simultaneous reduction of HC and NOx emissions using diesel extracts.