Under solvothermal reaction conditions, nitrobenzene is heated in the presence of aluminum chloride to yield a luminescent and paramagnetic low molecular weight polymeric material along with AlCl3·(H2O)6. MALDI mass spectral analysis demonstrates that the repeat unit consists of the biphenyl moiety (ONC6H3–ONC6H4). Four distinct fractions are isolated based on differential solubility characteristics. The primary differentiating features of these fractions appear to be their considerably different conjugation and branching characteristics. A radical mechanism, consistent with the formation of Wheland intermediates is proposed to account for the observed mass spec, IR, UV–Vis, EPR and size exclusion chromatographic data. Luminescence spectroscopy data is also provided demonstrating the white light emission exhibited by these polymers.