In this study, vinasse shell biochar (VS) was easily modified with phosphogypsum to produce a low-cost and novel adsorbent (MVS) with excellent fluoride adsorption performance. The physicochemical features of the fabricated materials were studied in detail using SEM, EDS, BET, XRD, FTIR, and XPS techniques. The adsorption experiments demonstrated that the adsorption capacity of fluoride by MVS was greatly enhanced compared with VS, and the adsorption capacity increased with the pyrolysis temperature, dosage, and contact time. In comparison to chloride and nitrate ions, sulfate ions significantly affected adsorption capacity. The fluoride adsorption capacity increased first and then decreased with increasing pH in the range of 3–12. The fluoride adsorption could be perfectly fitted to the pseudo-second-order model. Adsorption isotherms matched Freundlich and Sips isotherm models well, giving 290.9 mg/g as the maximum adsorption capacity. Additionally, a thermodynamic analysis was indicative of spontaneous and endothermic processes. Based on characterization and experiment results, the plausible mechanism of fluoride adsorption onto MVS was proposed, mainly including electrostatic interactions, ion exchange, precipitation, and hydrogen bonds. This study showed that MVS could be used for the highly efficient removal of fluoride and was compatible with practical applications.