The lignite boilers are designed for lower quality fuels, and often the ash is not utilized. This work assessed the impact of combustion of an herbaceous biomass with a low-quality Greek lignite on the quality of the resulting fly ash. Test results were compared with those of fly ash samples from an industrial facility using the same fuel qualities. Inductively coupled plasma-optical (ICP) emission spectroscopy, X-ray powder diffraction (XRD), and scanning electron microscope (SEM) analyses were performed on the collected samples. Despite the significantly higher contents of K, Na and S in the biomass, at a 50% co-firing thermal share, the major and minor oxides in the fly ash were comparable to the lignite fly ash quality. This is attributed to the high ash content of the lignite, the low ash content of the biomass, and the much higher heating value of the biomass. There were improvements in fly ash performance characteristics with the herbaceous biomass in the fuel blend. The initial setting time and volume stability evaluations were improved with the biomass in the fuel blend. The work supports efforts of good practices in ash management, social responsibility, a circular economy, power plant renewable energy operations, and co-firing herbaceous biomass fuels in lignite power plants.