The development of novel porous composite materials for organic dye degradation and removal has received increasing attention due to water contamination problem. In this paper, hydrothermal synthesized nano zeolite A have been encapsulated with porous periodic mesoporous organosilica (PMO) through a simple modified StÖber method an organosilane-directed growth-induced etching strategy, the obtained yolk-shell structured sample was further functionalized by the impregnation of copper, realizing the composite material with hierarchical porous and catalytic properties. The morphology, porosity and metal content of the zeolite Cu/A and Cu/A@Et-PMO were fully characterized. As compared to the parent material, the composite Cu/A@Et-PMO have an efficient adsorption and catalytic degradation performance on methylene blue (MB), the removal efficiency reached as high as 95% of 60 mg/L MB with 10min. These novel structured porous composites may have great potential for adsorption and degradation application including waste effluents.