The detailed ash transformation process during the combustion of agricultural biomass containing moderate to high amounts of P was studied in entrained flow conditions. The selected fuels were grass and brewer’s spent grain (BSG) containing a moderate and high amount of P in the fuel, respectively. The experiments were conducted in a lab-scale drop tube furnace at 1200 and 1450 °C. The residual chars, ashes, and particulate matter (PM) were collected and analyzed by scanning electron microscopy-energy-dispersive X-ray spectroscopy (SEM-EDS), X-ray diffraction (XRD), inductively coupled plasma atomic emission spectroscopy (ICP-AES) and ion chromatography (IC), and CHN-analysis. Additionally, the obtained results were interpreted through thermodynamic equilibrium calculations (TECs). For both fuels, P was primarily identified in the residual coarse ash (>1 μm) fractions. In contrast, a minor to moderate amount of fuel inherent P was detected in the fine particulate (<1 μm) fraction at 1200 and 1450 °C, respectively. For grass, the retained P in the residual coarse ash fractions was mainly identified as amorphous K–Ca–Mg-rich phosphosilicate melt. These phosphosilicates were most likely formed through the initial formation of molten K-rich silicates, with subsequent incorporation of Ca, P, and Mg. For BSG, a P–Si-rich fuel with moderate to minor amounts of Ca, Mg, and K, most P was retained in a Ca–Mg-rich phosphosilicate melt, likely originating from phytate-derived Ca–Mg phosphates interacting with fuel-inherent Si-rich particles. The results obtained from this study could be used to address the ash-related challenges and potential P-recovery routes during pulverized fuel combustion of P-containing biomass.