In earlier report, polydiacetylene vesicles were prepared from PCDA supramolecules, bearing terminal amido groups, display complete reversibility upon thermal stimulation. Most of the PCDA based vesicles show the thermal behavior from blue to red. Henceforth to switch over this unique property of PCDA, series of thermochromically reversible/irreversible polydiacetylene supramolecules (symmetric and unsymmetric) have been synthesized. The chromism property of these molecules is based on the hydrogen bonding and interaction of the functional group in backbone molecules. The color transition temperatures and thermochromic reversibility of the polymers are varied depended on the molecular structural variations. The polydiacetylenes with functional group derivatives stretch the complete thermochromic reversibility, while the main polymer π-system; it exhibited irreversible thermochromism, whereas the polymers attained from the different analogues are partially reversible. The variation of the linkers also allows the color transition temperature of the polydiacetylene to be tuned in the range of 20° C to over 90° C. The results provide a fundamental idea about the factors affecting the thermochromic properties of polymer π-system toward the development of materials for universal thermal indicators.