In EO polymer materials, the second-order nonlinear optic chromophores must be oriented in one direction in order to be electro-optically active. Interchromophore electrostatic interactions, which encourages the formation of non-active and light-scattering crystalline domains through the antiparallel stacking of dipoles, have long been an obstacle to the translation of large molecular optical nonlinearity into corresponding bulk nonlinearity. Great progresses have been made in the design and synthesis of chormophores with reduced electrostatic interactions. New effort toward the complete elimination of the destructive effect of the electrostatic forces is on the way. On the contrary, strong intermolecular electrostatic interaction (e.g. the force responsible for π-π stacking of conjugated systems) is often desired in LED, transistor and photovoltaic (PV) devices since high mobilities of the charge carriers are the key to their high performances and often come from ordered stacking of pi-conjugated systems. For PV applications, bi-continuous "bulk heterojunction" of electron donor (D) and acceptor (A) is ideal for efficient charge carrier generation, transport and collection. Differential electrostatic interactions between D and A is the key to the formation of such morphology. We have synthesized a novel type of block copolymer having a basic unit of D-B-A (B is a non-conjugate bridge) for solar cell application. D and A can be designed in such a way that D-D and A-A interactions are stronger than the D-A interaction, and therefore, have a strong tendency to phase separate.