Biochar, a low-density yet carbon-rich material derived from different organic materials pyrolyzed under low or no oxygen conditions, has been widely studied as a soil amendment, for greenhouse gas mitigation and in remediation of trace element-contaminated soils. Molecular speciation of biochar compounds has been challenging due to low solubility, aggregation, and immense compositional polydispersity that challenges nearly all mass spectrometry methods routinely applied to carbon-based organic materials. Through a combined technique approach that applies advanced analytical strategies, we provide bulk and molecular characterization of Kentucky bluegrass biochar that can be applied to any biomass or biochar sample. First, we characterize Kentucky bluegrass biochar chemical functional groups by solid-state magic-angle spinning dynamic nuclear polarization NMR (MAS-DNP NMR) and resolve aromatic and aliphatic signals from the pyrogenic material and intact plant material. Next, we isolate water-soluble biochar species by solid-phase extraction followed by Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) and identify highly polar, oxygen species across a wide carbon number range. Solvent fractionation of biochar further expands the compositional range and identifies condensed polycyclic aromatic species across nonpolar and polar classes detected by two ionization modes (-ESI and +APPI) by FT-ICR MS. Plotting biochar species with DBE versus carbon number highlights the pericondensed molecular structural motif that persists across numerous heteroatom classes and ionization modes. To the best of our knowledge, this is the first molecular level identification of nonfunctionalized PAHs in biochar extracts by APPI FT-ICR MS. Thus, we identify biochar species that span the same compositional space as coal, heavy oil asphaltenes, and coal tar and correspond to condensed ring PAHs.