One-dimensional organic nanowires provide a valuable platform for understanding emergent electronic phenomena in organic semiconductor materials. We have prepared a class of organic nanowires consisting of stacked pi-conjugated building blocks covalently attached to a solubilizing backbone. We have formed self-assembled monolayers from nanowires of various π-stack lengths and sequence contexts on gold substrates and characterized their properties with a range of techniques, including x-ray photoelectron spectroscopy (XPS), near-edge x-ray absorption fine structure spectroscopy (NEXAFS), and resonant photoemission spectroscopy (RPES). These studies have elucidated the nanowires’ electronic structure, geometric orientation at solid substrates, and interaction with the surrounding environment. Our findings hold significance both for fundamentally understanding nanoscale charge transport phenomena and for the development of new types of biological and molecular electronic devices.