Co-pyrolysis of plastic waste and wood biomass to recover valuable chemicals is a cost-effective waste-recycling technology. However, widely used organophosphate ester additives in plastic, such as tris(2-butoxyethyl) phosphate (TBEP), can form diverse phosphorus (P)-containing species. These P-containing compounds can pose new environmental challenges when the biochar is reused. In this study, a mixture of TBEP and lignin was used to simulate the feedstock of plastic waste and wood biomass, and the thermochemical behavior of TBEP in slow pyrolysis (20 K min(-1)) and fast pyrolysis at 400-600 °C was investigated. The results show that low temperature in fast pyrolysis favors the enrichment of P in char. Up to 76.6% of initial P in the feedstock is retained in the char resulting from 400 °C, while only 51% is retained in the char from 600 °C. Slow pyrolysis favors the formation of stable P species regardless of the temperature; only 7% of the P retained in the char is extractable from char from slow pyrolysis, while 20-40% of P can be extracted from char resulting from fast pyrolysis. The addition of CaCl2 and MgCl2 can significantly increase the fraction of P retained in the char by the formation of Ca, Mg-P compounds. Online TG-FTIR-MS analysis suggests that TBEP undergoes decomposition through different temperature-dependent pathways. The P-containing radicals react with the aromatic rings produced by the pyrolysis of lignin to form Ar-P species, which is an important factor influencing the distribution and stabilization of P in char.