Bimetallic MOFs have recently emerged as promising materials for wastewater treatment based on advanced oxidation processes. Herein, a new bimetallic MOF (FeCu-MOF) was fabricated by hydrothermal process. The structural, morphological, compositional and physicochemical properties of the as-synthesized bimetallic FeCu-MOF were characterized by XRD, FT-IR, SEM, TEM, BET, and XPS. TEM and XPS confirmed the homogeneous distribution of CuO2 nanoparticles in the as-synthesized materials. The result of wastewater treatment indicated that 100% of MB was removed by 6.0 mM PMS activated with 0.6 g/L of FeCu-MOF in 30 min. The high catalytic performance of FeCu-MOF was probably due to the accelerated electron and mass transfer resulting from the existence of a homogeneous distribution of unsaturated metal sites and an abundant mesoporous structure. The obtained results from the competitive quenching tests demonstrated that sulfate radicals (SO4•−) were the major species responsible for MB oxidation. In addition, hydroxyl (·OH) and singlet oxygen (1O2) also had a nonnegligible role in the MB removal. Interestingly, the addition of acetate ion (CHCOO−) promoted the removal of MB while other anions (including NO2−, H2PO4−, SO42−, HPO42−, and HCO3−) inhibited the MB removal. Furthermore, a possible mechanism based on both heterogeneous and homogeneous activation of PMS was proposed, along with the MB degradation mechanism.