We design amphiphilic di-block copolymers (P-b-F and P-b-C) tethered with stimuli-responsive ferrocene and coumarin hydrophobic pendants that exhibit chain collapse behaviour in response to light, redox and chemical cues, with subsequent transformation of the vesicles into micelles. Interestingly, the co-assembled vesicles of the polymer blend under orthogonal stimuli furnish self-sorted micelles and vesicles.