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In recent decades, advances in low NOₓ coal combustion and increasingly strict CO₂ reduction mandates have changed power plant boiler operations quite significantly. As a result of these necessary efforts, the characteristics of fly ash generated at many power plants have also changed. In particular, increases in unburned carbon content have been observed with detrimental implications on the utility of these fly ashes in concrete applications. Over the same time period, the combustion of biomass for energy generation has received increased attention due to the potential benefits of reducing CO₂ emissions and improved sustainability when compared to fossil fuel combustion. Biomass is directly burned, gasified, or co-fired with coal to achieve this goal. Currently, close to 120 million metric tons of coal combustion by products are produced in the U.S. annually. As with coal combustion, production of energy from biomass combustion/gasification results in significant by-product generation that must either be productively reused or geologically disposed. While much research effort has been devoted to understanding the properties and potential productive reuse alternatives for coal combustion residuals, relatively little work has been done on the by-products of biomass combustion. This study investigated the properties and engineering behavior of sixteen ash samples that were produced in eleven different power plants. Specifically, three high carbon content Class F fly ashes, eight coal and biomass co-fired ashes, three pure biomass ash samples, and two high quality, low carbon content ash samples, one of which is commercially marketed (for reference) were chosen. The various ash samples were characterized by means of: electron microscopy; laser diffraction and dry sieve particle size analysis; loss on ignition and total organic carbon analysis; specific surface area analysis; as well as x-ray fluorescence and x-ray diffraction. The ash samples were also investigated for their potential engineering application in the fired clay brick industry, as low-cost adsorptive agents, and in alkali activated geopolymer synthesis for geotechnical and geoenvironmental applications. Results from physical and chemical characterization of the ash samples show no significant differences between pure coal ash and coal co-fired with biomass ash samples from the same power plant. However, there are significant morphological, chemical, and mineralogical differences between coal ash and pure biomass ash. Unlike pure coal ash, biomass ash is not composed primarily of aluminosilicate glass cenospheres but rather consists mainly of charred, fibrous woody remnants with elevated calcite content as compared to coal ash. Bench scale fired bricks produced by partial replacement of clay material with high carbon coal ash, co-fired ash, and pure biomass ash, respectively, was successful. Physical properties of a number of the mix designs exceeded the highest ASTM weathering grade requirements. As sorptive agents, high carbon concentrates from coal and co-fired ash samples, along with all the biomass ash samples, showed significant uptake of lead. The unaltered as- received ash samples (i.e. no acid or steam activation) showed only moderate arsenic (V) and selenium (VI) sorption capacity. Finally, solidification/stabilization by geopolymerization of high carbon content, co-fired ash with as little as 3 molar NaOH in the activator solution was successful, possibly paving the way for various geotechnical and geoenvironmental applications in ground improvement and soil/ash-pond stabilization.