Liquid crystals comprising extended π-conjugated units work as semiconductors. On the other hand, ferroelectricity in liquid crystal systems is induced by molecular chirality in the classical concept. Moreover, ferroelectric columnar phases based on one-dimensional hydrogen-bonding chains and stacking of umbrella-shaped molecules have recently been studied to provide new insights into polarization in liquid crystal media. By incorporating electroactive π-conjugated units into the ferroelectric liquid crystal molecules, ferroelectricity can be coupled with electronic charge carrier transport in the one- or two-dimensional assemblies of π-conjugated units to create new functional materials and devices. In this chapter, π-conjugated ferroelectric liquid crystals with layer and columnar ordered structures are focused from a viewpoint of new phenomena based on electronic carrier transport coupled by spontaneous polarization. This coupling provides new electronic functions such as bulk photovoltaic effect, switched electronic transport, and polarization-induced charge carrier injection leading to polarized electroluminescence.