A recently developed extrography separation method fractionates petroleum asphaltenes based on their ionization efficiency, which correlates with polarity, aggregation tendency, and asphaltene structure (single-core or island versus multicore or archipelago). Archipelago asphaltenes were recently demonstrated to coexist with island structures in a variety of petroleum samples; however, archipelago compounds ionize much less efficiently than island compounds, making the former difficult to observe by mass spectrometry without prior separation. Highly processed coal-derived asphaltenes have been studied previously to reveal only small, single-core structure asphaltenes; however, the structure(s) of asphaltenes from unaltered coal extracts has not been extensively studied. Thus, this work focuses on the application of the extrography separation to an unaltered Illinois coal No. 6 asphaltene extract to reveal the coexistence of island and archipelago structural motifs by positive-ion (+) atmospheric pressure photoionization (APPI) Fourier transform ion cyclotron resonance mass spectrometry. Asphaltenes from a Wyoming crude oil sample are also characterized for comparison with coal asphaltenes. The results reveal that Wyoming crude oil asphaltenes contain mainly island species, whereas coal asphaltenes contain archipelago and island compounds with high oxygen content. The structural analysis is enabled by a new “multinotch” stored-waveform inverse Fourier transform isolation, which selectively isolates high-aromaticity precursor ions at each of several nominal mass ranges prior to fragmentation by infrared multiphoton dissociation, and enables unambiguous determination of island versus archipelago species in samples that contain compounds with high and low aromaticity. The more polarizable fractions from each asphaltene sample reveal low-aromaticity polyfunctional oxygenated species, with a solubility behavior consistent with asphaltenes but a compositional range typical of maltenes. These atypical asphaltene species, which ionize poorly, are hypothesized to participate in multiple hydrogen bonding interactions and thus exhibit strong adsorption on polar stationary phases such as SiO2. Furthermore, these polarizable polyfunctional species ionize preferentially as protonated cations by (+) APPI, accounting for their capability to hydrogen-bond in solution. Collectively, the results demonstrate the existence of archipelago structures in both coal and petroleum asphaltenes, along with polyoxygenated species with low aromaticity that behave like asphaltenes in terms of solubility, because they can establish stronger intermolecular forces such as hydrogen bonding.