In this review, we describe some of our recent approaches to the development of functional liquid-crystalline (LC) materials and fibrous aggregates. A variety of electro-active and photo-active π-conjugated molecules that exhibit nanostructured LC phases such as micellar cubic, columnar, and smectic structures have been designed and prepared. The formation of controlled phase-segregated structures has led to the efficient 1D and 2D transportation of charges. Redox-driven molecular shuttling for an LC bistable rotaxane has been achieved in the LC phase. Mechanoresponsive photoluminescent liquid crystals have also been developed. Moreover, we have demonstrated the formation of aligned electro-active fibrous aggregates either using liquid crystals as anisotropic templates or applied electric fields. These anisotropic self-assembled materials may have great potential applications as organic semiconductors, polarizers, sensors, and memories. This kind of approach to the use of self-organization processes for the development of functional molecules may open up new avenues in the fields of supramolecular chemistry and materials science.