The synthesis of a new azobenzene (azo)-containing main-chain crystalline polymer with reactive secondary amino groups in its backbone and photodeformation behaviors of its supramolecular hydrogen-bonded fibers are described.This main-chain azo polymer (namely Azo-MP6) was prepared via first the synthesis of a diacrylate-type azo monomer and its subsequent Michael addition copolymerization with trans-1,4-cyclohexanediamine under a mild reaction condition.Azo-MP6 was found to have a linear main-chain chemical structure instead of a branched one,as verified by comparing its 1H-NMR spectrum with that of the azo polymer prepared via the polymer analogous reaction of AzoMP6 with acetic anhydride.The thermal stability,phase transition behavior,and photoresponsivity of Azo-MP6 were characterized with TGA,DSC,POM,XRD,and UV-Vis spectroscopy.The experimental results revealed that it had good thermal stability,low glass transition temperature,broad crystalline phase temperature range,and highly reversible photoresponsivity.Physically crosslinked supramolecular hydrogen-bonded fibers with good mechanical properties and a high alignment order of azo mesogens were readily fabricated from Azo-MP6 by using the simple melt spinning method,and they could show reversible photoinduced bending under the same UV light irradiation and good anti-fatigue properties.