The sorption of hydrophobic organic compounds by natural organic matter is mainly regulated by its aromatic and aliphatic fractions, but it is not clear which fraction is more dominant. In this study, six types of Chinese tea leaves (three varieties of tender and three corresponding mature leaves) and their respective brewed ones were analyzed by elemental analysis, 13C NMR, and Fourier transform infrared attenuated total reflectance. Their sorption of phenanthrene was examined using a batch equilibration technique. The aromatic carbon content of tea leaves reduced while the aliphatic carbon content increased with increasing maturity and brewing. Sorption isotherms by all of the 12 tea sorbents were practically linear, showing a partition type sorption. The phenanthrene KOC (organic carbon-normalized sorption capacity) of the 12 sorbents ranged from 6960 to 32,900 mL/g, which increased with increasing aliphatic carbons and decreasing aromatic carbons in the tea leaves. The dissolved organic matter was released into solution from the sorbents during the sorption process, which could bind phenanthrene in the solution, and thereafter leading to underestimation of sorption capacity of the sorbents, but this did not change the correlation trends between KOC and functional carbon group content. Aliphatic fractions rather than aromatic moieties regulated the phenanthrene sorption of the tea leaf powders used in this study.