A superhydrophobic/hydrophilic asymmetric free-standing film has been created using layer-by-layer assembly technique. Poly(ethylene-imine)-Ag+ complex (PEI-Ag+) at pH 9.0 was assembled with poly(acrylic acid) (PAA) at pH 3.2 on a Teflon substrate to yield a micronanostructured surface that can be turned to be superhydrophobic after being coated with a low surface energy compound. Silver nanoparticle loaded free-standing film with one surface being superhydrophobic while the other surface is hydrophilic was then obtained after detachment from the substrate. The superhydrophobicity enabled the upper surface with anti-adhesion and self-cleaning properties and the hydrophilic bottom surface can release silver ions as antibiotic agent. The broad-spectrum antimicrobial capability of silver ions released from the bottom surface coupled with superhydrophobic barrier protection of the upper surface may make the free-standing film a new therapy for open wound.