The bisolute sorption and thermodynamic behavior of organic pollutants on low temperature biochars (LTB) at 300 °C and high temperature biochars (HTB) at 700 °C were determined to elucidate sorptive properties of biochar changed with pyrolytic temperatures. The structural characteristics and isotherms shape of the biochar were more dependent on the pyrolytic temperature than on the biomass feedstocks, which included orange peel, pine needle, and sugar cane bagasse. For LTB, the thermally altered organic matter colocalized with the carbonized matter, and the visible fine pores of the fixed carbons were plugged by the remaining volatile carbon. For HTB, most of the volatile matter was gone and the fixed matter was composed of fully carbonized adsorptive sites. Monolayer adsorption of 1-naphthol to HTB was dominant but was suppressed by phenol. In comparison, LTB displayed exceptional sorption behavior where partition and adsorption were concurrently promoted by a cosolute and elevated temperature. In addition to monolayer surface coverage, pore-filling mechanisms may contribute to the increase of adsorption fraction. Moreover, the entropy gain was a dominant force driving the partition and adsorption processes in LTB. Thus, the colocalizing partition phase and adsorptive sites in LTB are proposed to be in interencased states rather than in physical separation.