A novel nanostructure MoS2 nanoflowers anchoring iron(III)-based metal-organic framework MIL-101(Fe) [Fe3O(H2O)2Cl(O2C–C6H4−CO2)3], named MoS2-MIL-101(Fe), was prepared by growing MIL-101(Fe) crystals with as-prepared MoS2. Then, MoS2-MIL-101(Fe) was characterized through SEM, TEM, BET, XRD, DLS, and XPS. MoS2-MIL-101(Fe) possesses synergetic peroxidase-mimicking activity over individual MIL-101(Fe) and MoS2, which can catalyze the oxidation of TMB by H2O2 with a much stronger Vis-absorption. MIL-101(Fe) has a high porosity and large specific surface area for MoS2 to absorb H2O2 and TMB. Hydrophilic MIL-101(Fe) could prevent the aggregation of hydrophobic MoS2 in aqueous solution, which is beneficial for catalysis. In addition, anchored MoS2 brings mesopore and abundant exposed active units to the MIL-101(Fe) surface. The synergetic effects result in a highly enhanced catalytic performance. The Michaelis constant (0.008 mmol/L) of MoS2-MIL-101(Fe) for H2O2 is 462 times lower than that of HRP, showing its strong affinity with H2O2. On the basis, a sensitive method for H2O2 detection was proposed with a linear range of 0.01−20 μmol/L and a detection limit of 10 nmol/L. Considering H2O2 as product in the reaction of glucose catalyzed by glucose oxidase, a sensitive and selective method for glucose detection was proposed. The method can be used in blood glucose detection with good accuracy.