Organic molecules entrapped in biochar during pyrolysis and gasification of switchgrass have been studied using high-resolution mass spectrometry. Two solvent systems, toluene and a mixture of water/methanol, were used to extract hydrophobic aromatic compounds and hydrophilic polar compounds, respectively. Laser desorption ionization and atmospheric pressure photoionization were used for toluene extracts, while electrospray ionization was used for water/methanol extracts, followed by orbitrap mass spectrometric data acquisition. Molecular compounds previously known in bio-oils were observed for fast pyrolysis biochar, with phenolic and carbohydrate-derived compounds originating from the pyrolysis of lignin and holocellulose, respectively. In contrast, polycyclic aromatic hydrocarbons (PAHs) with various ring sizes were observed for gasification biochar and also for slow pyrolysis biochar in low abundance.