Charcoal (also referred to as black carbon) is produced by pyrolysis of vegetation and fossil fuels in the absence of oxygen. The charcoal beneath the soil is valuable evidence, apparently reflecting past human activities in the selection of biomass origin and the use of fire over millennia; thus, the compositional analysis of charcoal has been developed. Nuclear magnetic resonance (NMR) spectroscopy is regarded as one of the most powerful approaches, enabling the structural characterization of black carbon cross-linked framework and other organic components. While the utilization of solid-state NMR has been predominant for charcoal analysis owing to insolubility, solution-state NMR possesses better selectivity and sensitivity to analyse pyrolytic substituents adsorbed onto charcoal sites. Herein, the novel comparative profiling of pine and birch charcoal extracts was established using 1D and 2D solution-state NMR spectroscopy. The degradation of lignocellulosic compounds in wood was recorded in parallel to the increase in heat treatment temperatures, followed by the production of polycyclic aromatic hydrocarbons (PAHs). Moreover, archaeological samples from Degersjön and Gunnarsbyn (northern Sweden) – part of a larger study including NMR, FTIR and other analyses – were subsequently evaluated in order to ascertain their biomass origin and burning temperatures. This provides valuable molecular information to complement prehistoric and archaeological insight into human activities in those regions. This strategy contributes to a comprehensive understanding of the hidden history of human development, pioneering the widespread investigation of different vegetation charcoal extracts.