Phosphorus-modified biochars are considered as good materials for the removal of heavy metals from wastewater. However, the efficacy of ammonium polyphosphate-modified biochar in cadmium (Cd(II)) adsorption remains largely unknown. In this work, the biochar was respectively modified with ammonium polyphosphate (PABC), phosphoric acid (PHBC) and ammonium dihydrogen phosphate (PNBC) to enhance its adsorption performance for heavy metals from wastewater. The properties of biochar before and after modification and P speciation on the surface of the modified biochar were investigated with FTIR, SEM-EDS, XPS, XRD and 31P NMR, and the adsorption capacity was evaluated by batch adsorption experiments. The results demonstrated that the optimal adsorption performance could be achieved at the solution pH = 4, and the pseudo-second-order and Langmuir models could well describe the Cd(II) adsorption process. The maximum adsorption capacity of PABC, PHBC and PNBC for Cd(II) was 155, 138 and 99 mg g−1, which were 4.84, 4.32 and 3.10 folds that of original biochar, respectively. The 31P NMR showed that orthophosphate accounted for 82.1%, 62.8% and 54.5% of P in PABC, PHBC and PNBC, respectively, which decreased to 28.24%, 33.51% and 29.34% after Cd(II) adsorption, indicating that the orthophosphate ratio in P-modified biochar surface could significantly affect Cd adsorption by forming phosphate precipitate. This work implies that the PABC has greater potential in the removal of Cd from wastewater relative to PHBC and PNBC.