In this study, sorption coefficients (logKOC, n) for the binding of phenanthrene (PHE) to soil humins, insoluble fraction of soil humc substances (HS), were determined and relationship between the sorption coefficients and structural characteristics of the soil humins were investigated. The soil humins used in the present study were isolated from 7 different soils including 5 domestic soils, an IHSS standard and a peat soil, and characterized by elemental analysis and CPMAS C NMR method. C NMR spectral features indicate that the soil humins are mainly made up of aliphatic carbons (57.1~72.3% in total carbon) with high alkyl-C moiety, and the alkyl-C contents (CAl-H,C, %) was in order of granite soil Hu (26~42%) > volcanic ash soil, HL Hu (23.9%) > Peat Hu (14.0%). The results of correlation study show that a positive relationship (r = 0.77, p < 0.05) between organic carbon normalized-sorption coefficients (KOC, mL/g) and alkyl-C contents(CAl-H,C, %), while negative relationship (r = (-)0.74, p < 0.05) between Freundlich sorption parameter (n) and H,C-substituted aromatic carbon contents (CAr-H,C, %). The magnitude of KOC values are also negatively well correlated with polarity index (e.g., PI, N + O)/C) (r = (-)0.74, p < 0.1). These results suggest that the binding capacity (e.g., KOC) for PHE is increased in soil humin molecules having high contents of alkyl-C or lower polarity, and nonlinear sorption for PHE increased as the H,C-substituted aromatic carbon contents (CAr-H,C, %) in the soil humins increased. The PHE sorption characteristics on soil humins are discussed based on the dual reactive mode of sorption model.