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Conjugated rod-rod block copolymers (BCPs) have attracted considerable attention during the past decade as they possess both the interesting microphase-separated characteristics of BCPs and the excellent optoelectronic properties of conjugated polymers. As a consequence, impressive advances in conjugated rod-rod BCPs have been achieved both as model systems for systematic research on their crystallization and microphase separation and as promising materials for optoelectronic applications. After a brief overview of the phase behavior of coil-coil, rod-coil, and rod-rod BCPs and charge transport mechanism in conjugated polymers, we highlight recent developments in conjugated polythiophene-based rod-rod BCPs focusing on understanding and manipulating their crystalline structures and morphologies as well as their applications in organic photovoltaics and field-effect transistors. Finally, an outlook on the future of conjugated rod-rod BCPs is provided.