Fifteen neutral long‐chain‐substituted discotic nickel bis(1,2‐diphenyl‐1,2‐ethenedithiolene) complexes [Ni(dpedt)2], including thirteen new compounds, have been synthesized by new short and efficient synthetic pathways. Physical investigations show that these complexes are thermally stable, possess good electron‐accepting properties, and absorb light strongly in the near‐infrared spectral region. Electrochemical and optical properties of [Ni(dpedt)2] depend moderately on the functionalities attached to the phenyl rings of the complexes. Their LUMO and HOMO energy levels are in the range –4.7 to –5.0 and –5.7 to –6.0 eV, respectively. Two octa(n‐alkoxy)‐substituted complexes exhibit a columnar liquid crystalline phase with hexagonal symmetry. These highly soluble complexes are potential candidates for use as electron‐accepting and electron‐transporting materials for active layers in organic electronic applications, such as field‐effect transistors or photovoltaic devices.