We report the design, preparation of hierarchical hollow-pore nanostructure bilayer conjugated polymer films for high performance resistive memory devices. By taking the merits of chemical and structural stability of two-dimensional conjugated microporous polymer (2D CMP), a poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV) film with hollow surface was spin coated onto 2D CMP nanofilm directly, constructing the bilayer heterojunction. A two-terminal diode with a configuration of ITO/2D CMP/hollow MEH-PPV/Al was fabricated by employing the prepared bilayer heterojunction. The device poses flash feature with a high On/Off ratio (>105) and long retention time (>3.0×104 s), which is higher than most of the reported conjugated polymers memories. Our work offers a general guideline to construct high On/Off ratio polymer memories via hierarchical nanostructure engineering in memristive layer.