Thermochromism of a series of cast films of poly(3-alkylthiophenes) (P3ATs, A = hexyl, octyl, dodecyl, and hexadecyl) with different head-to-tail(HT) diad content (70-100%) was studied. The thermochromic behavior is found to be controlled by the HT diad content and the side chain length. P3ATs with moderate HT diad content give rise to a clear thermochromic isosbestic point irrespective of the length of the alkyl side chain. Regioregular polymers possessing a >90% HT diad content exhibit either a continuous thermochromic blue shift or an isosbestic point, depending on the alkyl side chain length. The different thermochromic characteristics are attributed to subtle morphological differences between the polymers. DSC and X-ray diffraction studies indicate that P3AT samples with moderate HT regularity are formally amorphous with a quasi-ordered phase dispersed in continuous disordered domains. P3ATs with high HT regularity consist of crystalline, quasi-ordered, and disordered phases. For polymers with short alkyl side chains, these phases equilibrate with each other and destroy the thermochromic isosbestic point. Polymers with long alkyl side chains melt at much lower temperature and are converted directly between the crystalline and disordered phases.