Composite structures of aligned and orientation-ordered quasi-one-dimensional CdS micro/nanostructures on CdSe substrates of different shaped nanostructures have been synthesized by using two-step thermal evaporation processes. The CdSe substrate crystalline orientations and local temperatures play their roles in the CdS nanostructure growth step, which is in some contrast with the vapor-liquid-solid (VLS) growth mechanism. Micro-photoluminescence measurements show strong luminescence responses on the six-fold symmetrical CdSe/CdS nanostructure. Controllable growth on various shaped substrates may find applications in obtaining many other aligned orientation-ordered hetero-nano/microstructure materials.