To control the self-assembled morphology of block copolymers (BCPs), a series of BCPs were synthesized and post-functionalized via click chemistry. More specifically, polystyrene-b-poly(allyl glycidyl ether)s (PS-b-PAGEs) were synthesized via the anionic polymerization of styrene and subsequent catalyzed ring-opening polymerization of the second PAGE block. Thiol窶兎ne click chemistry was utilized for the post-functionalization of the resulting polymers. To investigate the effects of functional side-chains on the interaction between segments, the Flory窶滴uggins interaction parameter マ� was estimated using the radon phase approximation method. The significant increases and decreases in the effective マ� (マ㌃ff) values obtained suggested that the introduction of functional groups significantly influenced マ㌃ff. Moreover, the morphologies of the synthesized BCPs were then investigated using X-ray scattering and transmission electron microscopy, and it was found that the morphology was also affected by the introduction of functional groups.