Supramolecular azopolymers were prepared through strong hydrogen bonding interaction between pyridine moiety
of poly (4-vinylpyridine) (P4VP) and phenol moiety of 4-nitro- 4’-hydroxyazobenzene (AzoOH). A multilayered composite film with supramolecular azopolymers as a recording layer and polyvinyl alcohol (PVA) as a spacing layer was prepared through alternately stacking. Under two-photon excitation, azobenzene chromophore can be orientated perpendicularly to the polarization direction of the writing beam via trans-cis-trans photoisomerization, yielding optical birefringence. Polarization-multiplexed and multilayered optical data storage were demonstrated by encoding two letters in the same region of each of the two layers based on the property.