A pentapeptide sequence was functionalized with an asymmetric arylated methyl-viologen (AVI3D2) and through controllable β-sheet self-assembly, conductive nanofibers were formed. Using a combination of spectroscopic techniques and conductive atomic force microscopy, we investigated the molecular conformation of the resultant AVI3D2 fibers and how their conductivity is affected by β-sheet self-assembly. These conductive nanofibers have potential for future exploration as molecular wires in optoelectronic applications.