To investigate the effect of pyrolysis temperature on the adsorption behavior of the emerging organic pollutant tris-(1-chloro-2-propyl) phosphate (TCIPP) on biochar, corn stover was used as raw materials to prepare biochars at different pyrolysis temperatures (250, 350, 500, 700 °C) through limited oxygen carbonization. Elemental analysis, Boehm titration, FTIR, XPS, and other analytical methods were used to reveal the effect of pyrolysis temperature on the physicochemical properties of biochar and its mechanism of TCIPP adsorption. The results showed that the pyrolysis temperature had a significant impact on the physicochemical properties of biochar. As the pyrolysis temperature increases, the specific surface area of biochar rises from 3.083 m2/g to 435.573 m2/g, the pH value increases from 6.60 to 10.66, the mass percentage of C increases from 63.10 to 80.58%, and the mass percentage of O decreases from 26.42 to 9.20%. Additionally, the hydrophobicity and aromaticity of biochar also increase with rising pyrolysis temperature, while its polarity decreases. Boehm titration, FTIR, and XPS analysis showed that the total amount of functional groups on the surface of biochar decreased relatively with increasing temperature. Functional groups such as -OH, C = C/C = O, and C-O-C participated in the adsorption of TCIPP on biochar, and ester groups were produced after adsorption. The adsorption process of TCIPP on biochar fits best with the pseudo-second-order equation, indicating that the adsorption process is mainly chemical adsorption, and the main rate-controlling stage is intraparticle diffusion. The isothermal adsorption results were more in line with the Temkin model, indicating that the adsorption process of TCIPP on biochar was mainly surface adsorption. As the pyrolysis temperature increases, the maximum adsorption capacity of biochar increases from 0.8837 mg/g to 2.2574 mg/g. The adsorption process of TCIPP on biochar mainly included pore filling, hydrogen bonding, P-π interaction, hydrophobic interaction, and electrostatic attraction. Among them, pore filling, P-π interaction, and hydrophobic interaction were significantly enhanced with increasing temperature, while hydrogen bonding was relatively weakened. This study will provide a theoretical basis and technical support for the removal of TCIPP from water using biochar adsorption.