We report the characterization of partial intercalation of 4-nitrobenzylamine (4-NBA) into edge-plane or edge-plane-like defect sites on the surface of both graphite powder and "bamboo-like" multiwalled carbon nanotubes (MWCNTs) using X-ray photoelectron spectroscopy (XPS). By comparing the XPS spectra of 4-NBA derivatized graphite powder and MWCNTs with that of graphite powder treated with benzylamine in a similar fashion, we conclude that benzylamine itself does not undergo partial intercalation. Using in situ atomic force microscopy, we are able to observe the partial intercalation of 4-NBA into an edge-plane-like "step" defect on the surface of a highly ordered pyrolytic graphite crystal in real time. Together these observations provide further evidence for the partial intercalation of 4-NBA and lead us to propose a new hypothesis to explain this phenomenon.