Disordered polymethacrylonitrile (PMAN) carbon monoliths have been studied as potential tailored electrodes for lithium ion batteries. A combination of electrochemical and surface spectroscopie probes have been used to investigate irreversible loss mechanisms. Voltammetric measurements show that Li intercalates readily into the carbon at potentials IV positive of the reversible Li potential. The coulometric efficiency rises rapidly from 50% for the first potential cycle to greater than 85% for the third cycle, indicating that solvent decomposition is a self-limiting process. Surface film composition and thickness, as measured by x-ray photoelectron spectroscopy (XPS) and secondary ion mass spectrometry (SIMS), does not vary substantially when compared to more ordered carbon surfaces. Li+ profiles are particularly useful in discriminating between the bound states of Li at the surface of solution permeable PMAN carbons.