Increasing the adsorption capacity and reducing the energy consumption of sludge biochar during preparation is important. In this study, a new modification method was developed to prepare phosphomolybdic acid-modified sludge biochar through the low-temperature pyrolysis of sewage sludge using phosphomolybdic acid as a modifier. Tetracycline was used to assess the adsorption performance of sludge biochar, and phosphomolybdic acid-modified sludge biochar was prepared at different temperatures. The results showed that the adsorption capacity of sludge biochar improved from 84.49 to 120.86 mg/g through modification with phosphomolybdic acid at 200 °C. The maximum adsorption capacities of phosphomolybdic acid-modified sludge biochar (200 °C pyrolysis temperature) at 298, 308, and 318 K were 283.87, 421.39, and 545.48 mg/g, respectively. Both liquid film and intraparticle diffusion were the main rate-limiting steps of tetracycline adsorption by phosphomolybdic acid-modified sludge biochar. Furthermore, the adsorption of tetracycline by phosphomolybdic acid-modified sludge biochar was mainly attributed to π-π interactions, electrostatic interactions, hydrogen bonding, and pore filling.