Polycyclic aromatic hydrocarbons (PAHs) are persistent organic pollutants in the environment, which are teratogenic, carcinogenic, and mutagenic. Co-contamination of PAHs and heavy metal commonly exists in soil. In this study, 20 types of soils with different properties in China were collected and comprehensively characterized. Phenanthrene (Phe) and Cu (II) were selected as representatives of PAHs and heavy metals, respectively. The adsorption-desorption behaviors of Phe under Phe contamination and Cu (II)-Phe co-contamination in 20 types of soils were studied. The adsorption-desorption behaviors of Phe in 20 types of soils varied greatly, and adsorption of Phe in the soils followed both linear partitioning and nonlinear surface adsorption. Soil organic matter (SOM) plays an important role in the adsorption-desorption behavior of Phe. When the concentrations of Phe were >50 μg/L, soft carbon (SC) fraction of SOM not black carbon (BC) contributed more to the adsorption of Phe. Soil dissolved organic matter (DOM), especially fulvic acid and humic acid fractions, contributes to the adsorption of Phe. Under the effect of Cu (II) (60 mg/L in solution), the adsorption capacity of soil for Phe increased, which possibly resulted from lowered pH, the existence of the cation-π bonding and the "bonding bridge" effect. The systematic investigation of adsorption-desorption behaviors of Phe in soils under heavy metal-PAHs co-contamination will provide a scientific basis for the calculation of soil environmental capacity in the future.