Hydrolyzed AlTi species are essential metal-based coagulants in a coagulation process to remove nanoplastics (NPs). Understanding the molecular interactions between hydrolyzed AlTi species and NPs is key to promoting coagulation efficiency. In this study, the coagulation performance and intrinsic mechanism of different AlTi species (including monomeric AlTi and polymeric AlTi species-Al13Ti13) for NPs removal were systematically investigated. We found that the polymeric AlTi species exhibited higher turbidity removal (95.0 %) and lower residual Al content (20.67 μg/L) at a low dosage over monomeric AlTi species. Al13 and Al13Ti13 formed by in situ hydrolysis were the dominant species to destabilize and aggregate NPs at pH 6. Main coagulation mechanisms were dominated by charge neutralization, complexation between the aliphatic CH of NPs and Al/Ti-OH, and cation-π interaction between polycations and the aromatic structure of NPs. The preformed Al13Ti13 showed multiple positive charge binding sites assisting its easy adsorption on NPs by electrostatic attraction, and then formed microscale aggregates through charge neutralization or intermolecular interaction. The preformed Al13Ti13 demonstrated a high stability and coagulation performance with respect to pH changes in raw water, whereas the promotion of μ-OH bridges dissociation by OH− and the presence of electrostatic repulsion significantly decreased the NPs removal by monomeric AlTi at high pH. This study provides valuable theoretical insights into the interaction between NPs and various hydrolyzed AlTi species.