A linear supramolecular polymer has been constructed from self-assembly of two complementary homoditopic monomers, an azobenzene-bridged pillar[5]arene dimer and a bisammonium salt, at high concentration based on the pillar[5]arene/secondary ammonium salt molecular recognition motif. This supramolecular polymer exhibited photo and pH dual-responsiveness. Polymer–oligomer and polymer–monomer transitions were reversibly regulated by UV/vis light irradiation and changing the solution pH, respectively. Furthermore, a photo-responsive supramolecular crosslinked liquid-crystalline polymer network based on the host–guest interactions between the azobenzene-bridged pillar[5]arene dimer and a secondary ammonium salt-functionalized poly(methyl acrylate) was fabricated.