Carbonaceous materials like biochars are increasingly recognized as effective sorbent materials for sequestering organic pollutants. Here, we study sorption behavior of two common hydrophobic organic contaminants 2,2',5,5'-tetrachlorobiphenyl (CB52) and phenanthrene (PHE), on biochars and other carbonaceous materials (CM) produced at a wide range of conditions and temperatures from various feedstocks. The primary aim was to establish structure–reactivity relationships responsible for the observed variation in CM and biochar sorption characteristics. CM were characterized for their elemental composition, surface area, pore size distribution, aromaticity and thermal stability. Freundlich sorption coefficients for CB52 and PHE (i.e. LogKF,CB52 and KF,PHE, respectively) to CM showed a variation of two to three orders of magnitude, with LogKF,CB52 ranging from 5.12 ± 0.38 to 8.01 ± 0.18 and LogKF,PHE from 5.18 ± 0.09 to 7.42 ± 1.09. The highest LogKF values were observed for the activated CM, however, non-activated biochars produced at high temperatures (>700 °C) sorbed almost as strongly (within 0.2–0.5 Log units) as the activated ones. Sorption coefficients significantly increased with pyrolysis temperature, CM surface area and pore volume, aromaticity, and thermal stability, and decreased with H/C, O/C, (O + N)/C content. The results of our study contribute to the understanding of processes underlying HOC sorption to CM and explore the potential of CM as engineered sorbents for environmental applications.