In order to improve the efficiency of biogas fermentation and biogas yields, the influence of different phosphorus potassium powder as the functional catalysts of biogas fermentation on anaerobic fermentation of cow dung was explored. Eight treatments were contained as follows: no addition（CK）, the addition of 2.5%（T1）, 5.0%（T2）, 7.5%（T3）, 10.0%（T4）Yunnan microcrystallization phosphate powder, 5.0%（T5）Henan microcrystallization phosphate powder, 5.0%（T6）Yunnan common phosphate powder, and 5.0%（T7）Henan microcrystalline muscovite rock. Results indicated that: with the increase of microcrystalline phosphate powder concentration, the ultimate production of biogas was improved significantly. Adding 7.5% microcrystallization phosphate powder results in the fastest anaerobic fermentation starting, the most biogas yield, and CH4 volume fraction was up to 62.5%, the removal rate of VS reached 61.99%, the chemical oxygen demand (COD) was 4871.4mg/L, the volatile fatty acid (VFA) was 469.9mg/L respectively. As microcrystalline phosphate powder concentration was increased as high as 10.0%, the ultimate accumulative biogas production was inhibited to 317.63mL/g. Adding microcrystallization phosphate powder of 7.5% was considered as the appropriate amount to improve the anaerobic digestion of cow manure. The microcrystalline grinding technology enhanced the nutrient release from the phosphate rock. Thus, it was significant to exploit and utilize the phosphate rock. This study provided a theoretical basis for developing a high efficient biogas catalysts formula and sustainable agriculture.