ESM/MIL-100(Fe) composite membranes were prepared on the egg shell membrane by layer by layer assembly method. The scanning electron microscopy results show that the MIL-100(Fe) is uniformly deposited on the ESM fiber surface, and the quantity of ESM/MIL-100(Fe) can be adjusted by assembly cycles. The composition of ESM cannot be destroyed by the assembly process from the FT-IR results. In the present of H2O2, above 98% RhB solution can be degraded by the ESM/MIL-100(Fe) samples with 10, 20 and 30 assembly cycles. By using the ESM support, both of the MIL-100(Fe) deposition and ESM/MIL-100(Fe) recycle can be easily conducted.