We investigate the effects of solvents on structure, morphology and photophysical properties of micelle-like assemblies of an azochromophore-functionalized polydiaacetylene (polyAzoDA) and polymerized tricosa-10,12-diynoic acid (polyTDA) for comparison Using mixtures of water with glycol, DMSO, ethanol and THF, we systematically vary the solubility parameters and observe blue-to-red color changes of polydiacetylenes Teas plots are used to estimate the strength of polymer solvent interactions and explain the properties of polyAzoDA supramolectilar assemblies in different solvent environments In poor solvents, polyAzoDA forms rod-like micelles and the photoisomerization is strongly hindered by the aggregation of azo chromophores At increasing content of Organic solvents, polyAzoDA becomes gradually swollen, as indicated by the onsets of blue-to-red color changes, starting trans-cis isomerizations of the azo groups, and changes of the structures as seen in SEM images At huge ethanol content, we observe that photoisomerization of azobenzene groups induces a morphological transition and a color change of the polydiacetylene backbone.