Rod-coil block copolymers are self-assembling polymers that combine the physics of orientational ordering of rodlike polymers and the microphase separation of coil-coil block copolymers. Several new solid-state morphologies were observed in a series of anionically synthesized model poly(hexyl isocyanate-b-styrene) rod-coil diblock copolymers examined by transmission electron microscopy and selected-area electron diffraction. The rod-coils formed smectic C-like and O-like morphologies with domain sizes ranging from tens of nanometers to almost 1 micrometer, Both structural and orientational changes were found for increasing rod volume fractions. In addition, some morphologies exhibited spontaneous long-range orientational order over many tens of micrometers.