A brand new sandwich-type poly(furfuryl alcohol) (PFA) nanostructure as well as ordered PFA nanofiber arrays has been successfully obtained through a novel two-step polymerization method by using a porous alumina membrane as the template, This novel structure is made tip of ordered PFA nanopillars supported by two PFA films on the top and bottom. The thickness of the PFA films oil both sides could be adjusted from several micrometers to tens of micrometers, and the flexibility of the membrane Could be controlled in a certain range. This sandwich-type polymer nanostructure can be used as ail effective template for constructing other ordered porous films resembling the structure of the parent alumina membrane, and in this study, ordered porous titania membrane has been successfully obtained. Theoretically, many other novel porous (or meso- and macro-mixed porous) materials could be synthesized through this novel template.