For the construction of hierarchical superstructures with biaxial anisotropic absorption, a newly synthesized diacetylene-functionalized bipyridinium is self-assembled to use an electron-accepting host for capturing and arranging guests. The formation of the donor-acceptor complex triggers an intermolecular charge transfer, leading to chromophore activation. Polarization-dependent multichroic thin films are prepared through a sequential process of single-coating, self-assembly, and topochemical polymerization of host-guest chromophores. Molecular packing structures constructed in the single-layer optical thin film possess orthogonal absorption axes for two different wavelengths. By tuning the linear polarization angle, the color of the optical thin film can be intentionally controlled. This single-layered multichroic film provides a new pathway for the development of anticounterfeiting and multiplexing encryptions.