The cation-directed self-assembly process has emerged as a fascinating approach for constructing supramolecular architectures and manifested a diverse range of assembly related applications. Herein, we synthesized a macrocyclic structure containing bis-amidopyridine and photopolymerizable diacetylene template, PyMCDA. Owing to the metal coordination affinity of bis-amidopyridine and the π-π stacking characteristic of diacetylene template and complementary to the cyclic molecular framework, Cs+-directed organic nanotubes are generated via unidirectional self-assembly of PyMCDA. The monomeric PyMCDA nanotubes are transformed into the covalently cross-linked chromogenic polydiacetylene nanotubes (PyMCPDA-Cs+) by UV-promoted topochemical polymerization. The result of a metal-ligand coordination characteristic, geometric parameters in solid-state assemblies, and topochemical polymerization behavior reveals a generation of Cs+ ion inserted nanotubes. Interestingly, PyMCDA-Cs+ nanotubes display thermochromic property with a brilliant blue-to-red color transition.