We investigated the mechanisms of Hg sorption onto biochars produced from Brazilian pepper (BP; Schinus terebinthifolius) at 300, 450, and 600 °C using different analytical techniques. The Hg sorption capacity of BP300, BP450, and BP600 was 24.2, 18.8, and 15.1 mg g(-1) based on Langmuir isotherm. FTIR data suggested the participation of phenolic hydroxyl and carboxylic groups in Hg sorption by biochars. XPS analysis showed that 23-31% and 77-69% of sorbed Hg was associated with carboxylic and phenolic hydroxyl groups in biochars BP300-450, whereas 91% of sorbed Hg was associated with a graphite-like domain on an aromatic structure in BP600 biochar, which were consistent with flow calorimetry data. Based on flow calorimetry, sorption of K and Ca onto biochar was exchangeable with the molar heat of sorption of 3.1 kJ mol(-1). By comparison, Hg sorption was via complexation with functional groups as it was not exchangeable by K or Ca with molar heat of sorption of -19.7, -18.3, and -25.4 kJ mol(-1) for BP300, BP450, and BP600. Our research suggested that Hg was irreversibly sorbed via complexation with phenolic hydroxyl and carboxylic groups in low temperature biochars (BP300 and BP450) and graphite-like structure in high temperature biochar (BP600).