The method of carbonizing biomass using di-(2-Ethylhexyl) phosphoric acid and tributyl phosphate impregnation (SICB) was studied in this research. SICB combines the benefits of an extractant and an ion exchange resin. The adsorption and desorption properties of vanadium were investigated, and the adsorption mechanism was analyzed. The results showed that the carrier was first prepared at a temperature of 1073.15 K using sawdust as a biomass substitute and then cooled to room temperature. The best adsorption performance was obtained by impregnating the carriers with di-(2-Ethylhexyl) phosphoric acid and tributyl phosphate for 60 min. The vanadium adsorption rate of 98.12% was achieved using the biomass at an initial V(IV) solution concentration of 1.1 g/L, a pH value of 1.6, and a solid-to-liquid ratio of 1:20 g·mL for 24 h. Using 25 wt.% sulfuric acid solution as desorbent, the desorption rate of vanadium was as high as 98.36%. The analysis showed that the adsorption of vanadium by SICB was chemisorption, and the adsorption process was more consistent with the proposed second-order kinetic equation. Therefore, SICB has high selectivity and high saturation capacity because of the mesopores and micropores produced by carbonization.