Charged block copolymers are promising materials for next-generation battery technologies and soft electronics. Although once it was only possible to prepare randomly organized structures, nowadays, well-ordered charged block copolymers can be prepared. In addition, theoretical and experimental analyses of the thermodynamic properties of charged polymers have provided insights into how to control nanostructures via electrostatic interactions and improve the ionic conductivity without compromising mechanical strength, which is crucial for practical applications. In this Account, we discuss methods to control the self-assembly and ion diffusion behavior of charged block copolymers by varying the type of tethered ionic moieties, local concentration of embedded ions with controlled electrostatic interactions, and nanoscale morphology. We discuss with particular emphasis on the structure-transport relationship of charged block copolymers using various ionic additives to control the phase behavior electrostatically as well as the ion transport properties. Through this, we establish the role of interconnected ionic channels in promoting ion-conduction and the importance of developing three-dimensional interconnected morphologies such as gyroid, orthorhombic Fddd (O70) networks, body-centered cubic (bcc), face-centered cubic (fcc), and A15 structures with well-defined interfaces in creating less tortuous ion-conduction pathways. Our prolonged surge and synthetic advances are pushing the frontiers of charged block copolymers to have virtually homogeneous ionic domains with suppressed ion agglomeration via the nanoconfinement of closely bound ionic moieties, resulting in efficient ion conduction and high mechanical strength.Subsequently, we discuss how, by using zwitterions, we have radically improved the ionic conductivity of single-ion conducting polymers, which have potential for use in next-generation electrochemical devices owing to the constrained anion depletion. Key to the improvement stems from hierarchically ordered ionic crystals in nanodomains of the single-ion block copolymers through the self-organization of the dipolar/ionic moieties under confinement. By precisely tuning the distances between ionic sites and the dipolar orientation in the ionic domains with varied zwitterion contents, unprecedented dielectric constants close to those of aqueous electrolytes have been achieved, leading to the development of high-conductivity solid-state single-ion conducting polymers with leak-free characteristics. Further, using these materials, low-voltage-driven artificial muscles have been prepared that show a large bending strain and millisecond-scale mechanical deformations at 1 V in air without fatigue, exceeding the performance of previously reported polymer actuators. Finally, smart multiresponsive actuators based on tailor-made charged polymers capable of programmable deformation with high force and self-locking without power consumption are suggested as candidates for use in soft robotics.