Although there has been substantial research done on adsorption of metals/metalloids by Al (oxy)hydroxides, little is known regarding the adsorption of polyaromatic hydrocarbons (PAHs) on Al (oxy)hydroxides, especially those formed in the presence of organic acid. This paper investigated the adsorption of phenanthrene on Al (oxy)hydroxides formed with initial tannate/Al molar ratios (MRs) 0, 0.001, 0.01, and 0.1 (referred to MR0, MR0.001, MR0.01, and MR0.1, respectively) through batch adsorption experiments and FTIR study. The results showed that Al (oxy)hydroxides were important sorbents for phenanthrene. The adsorption kinetic data were fitted well with the pseudo-second-order equation. According to a modified Freundlich model, the adsorption capacities of Al (oxy)hydroxides followed a descending order of MR0.1 > MR0 ≥ MR0.01 > MR0.001, which was inconsistent with the organic carbon content in the Al (oxy)hydroxides. Adsorption capacity correlated with the specific surface area, micropore area, and micropore diameter of Al (oxy)hydroxides, yet the relationships were not statistically significant (P > 0.05). FTIR results showed that physical interaction was essential in phenanthrene adsorption onto the Al (oxy)hydroxides, which could be explained by an entropy-driven process. Surface hydrophobicity of Al (oxy)hydroxides played a key role in phenanthrene adsorption. Additional π–π electron donor–acceptor interaction of phenanthrene (acting as electron donor) with aromatic ring of tannic acid (electron acceptor) could be also important in phenanthrene adsorption by high MR Al (oxy)hydroxides, yet it needs further study. The findings obtained in the present study are of fundamental significance in understanding the mechanism of immobilization of PAHs in low organic matter but oxide-rich soils.