Phosphorus is a depletable resource, and the consumption of phosphorus fertilizer increases with the growing population size. Phosphorus recycled from incinerated sludge ash can be a complement to phosphatic fertilizers in districts suffering from phosphorus resource shortages (e.g., Germany, Japan, and Sweden). The apatite inorganic phosphorus (AP) content in incinerated sludge ash is a key factor influencing the recoverability and bioavailability. Biomass straw is rich in calcium and magnesium minerals and can be used as an additive to be blended with sludge to increase the AP content. However, most of the current studies added excessive amounts of calcium-based or biomass additives, and the bioavailability of various Ca-Mg-P minerals generated after the addition of biomass has not been systematically discussed. In this study, the changes of the phosphorus form in the mixed sludge and biomass with Ca/P in the range of 1.0-2.5 are studied, and the influence of temperature and additives on the phosphorus form and the bioavailability of phosphorus in the ash samples are discussed by combining X-ray diffraction and citric acid (CA) leaching experiments. The AP content is very low in the residue of the sludge or corn straw (CS) that has been burned individually. The sludge and the blended sludge and CS were incinerated at various temperatures. As the incineration temperature increased, the conversion of non-apatite inorganic phosphorus (NAIP) to AP was promoted, but the bioavailability did not change until 1050 °C for samples with a Ca/P of 2.5. In the range from 750 to 950 °C, higher temperature promotes the formation of Ca2P2O7 and CaP2O6. CaP2O6 is insoluble in CA; thus, the bioavailability changes little from 750 to 950 °C, although the AP content increases. With the increase of Ca/P, the conversion of NAIP to AP and the bioavailability of phosphorus were promoted. For the blended sludge and CS ash, Ca7Mg2P6O24 appears at 950 and 1050 °C and the bioavailability also increases.