Highly Ordered <i>n</i>/<i>p</i>‑Co-assembled Materials with Remarkable Charge Mobilities López-AndariasJavier RodriguezMaría José AtienzaCarmen LópezJuan Luis MikieTsubasa CasadoSantiago SekiShu CarrascosaJosé L. MartínNazario 2015 Controlling self-organization and morphology of chemical architectures is an essential challenge in the search for higher energy-conversion efficiencies in a variety of optoelectronic devices. Here, we report a highly ordered donor/acceptor functional material, which has been obtained using the principle of ionic self-assembly. Initially, an electron donor π-extended tetrathiafulvalene and an electron-acceptor perylene-bisimide were self-organized separately obtaining <i>n</i>- and <i>p</i>-nanofibers at the same scale. These complementary <i>n</i>- and <i>p</i>-nanofibers are endowed with ionic groups with opposite charges on their surfaces. The synergic interactions establish periodic alignments between both nanofibers resulting in a material with alternately segregated donor/acceptor nanodomains. Photoconductivity measurements show values for these <i>n</i>/<i>p</i>-co-assembled materials up to 0.8 cm<sup>2</sup> V<sup>–1</sup> s<sup>–1</sup>, confirming the effectiveness in the design of these heterojunction structures. This easy methodology offers great possibilities to achieve highly ordered <i>n</i>/<i>p</i>-materials for potential applications in different areas such as optoelectonics and photovoltaics.