In this study, a novel MIL-100(Fe)@TiO2 composite was synthesized and used as the adsorbent to remove Rhodamine B from synthetic wastewater through adsorption and photocatalytic degradation. The composite was synthesized successfully using solvothermal methods. MIL-100(Fe)@TiO2 composite has excellent adsorption and photodegradation capability for Rhodamine B removal. The reusability of the materials was observed, with the conclusion that the material still had good adsorption and photocatalytic performance after five cycles of consecutive experiments. The adsorption isotherm, kinetic, and thermodynamic studies of the removal of Rhodamine B were also conducted. The Langmuir model represented the adsorption equilibrium data better than other models. The kinetics of adsorption of Rhodamine B was presented well by pseudo-first-order. The thermodynamic study verified that the physisorption mechanism was more dominant than chemisorption. The addition of Fenton was also proven to be successful in increasing the photocatalytic abilities of the synthesized materials.