A titanium-based Fenton-like heterogeneous catalyst was synthesized from titanium dioxide (TiO2), MIL-125(Ti), and Ti3C2 MXene for degrading the notorious Congo red (CR). The successful combination of the titanium components was assured by bountiful characterization apparatuses. Optimization of the finest conditions of the Fenton-like degradation of CR dye was performed by studying the impact of the pH and temperature of the catalytic system, the dosage of TiO2/MIL-125(Ti)@Ti3C2, the concentrations of hydrogen peroxide (H2O2) and CR, and the mass ratio between the catalyst’s components. A kinetic study was executed on the degradation of CR and H2O2 during a reaction time of 60 min using First-order and Second-order models. The degradation pathway of CR by TiO2/MIL-125(Ti)@Ti3C2 was investigated by the scavenging test. Additionally, Adsorption and catalytic degradation mechanisms were resumed using X-Ray Photoelectron Spectroscopy (XPS) analysis. The cycling test proceeded on TiO2/MIL-125(Ti)@Ti3C2 for five succeeding Fenton-like degradation runs of CR dye. Ultimately, the Ti-based heterogeneous catalyst exhibited superior adsorption and Fenton-like degradation performances toward the anionic dye with a good recyclability feature.