On the other hand, exploring the morphologies of conjugated rod–coil block copolymers in the confined geometry is of great importance for their applications in nanodevices, such as polymer brushes, nanofibers, and nanowires. The control of nanosize domain within the exciton diffusion length and the aligned direction of conjugated rods are the key issues for enhancing their optoelectronic device performance. The self-organized domains of block copolymers offer switch-like control on material functionalities by the relevant order–disorder or order–order transitions. The incorporation of a conjugated polymer rod moiety into block copolymers renders various morphologies to tune the electronic and optoelectronic properties. A further introduction of environmentally stimuli coil by block or graft-sequences can provide novel multifunctional sensory polymers with response to pH, temperature, light or metal ion-strength. It is expected that novel multifunctional sensory devices can be produced by the soft-patterning techniques with conjugated rod–coil block copolymers, such as micro-contact printing and nano-imprinting. This review shows how the interaction of chemistry, physics, and engineering in the conjugated rod–coil block copolymers, may spark future development of nanostructured polymers for multifunctional applications.