Insights from the molecular-level mechanism of sorption of organophosphate esters (OPEs) on carbon nanotubes (CNTs) can further our understanding of the fate and transport of OPEs in the environment. The motivation for our study was to explore the sorption process of OPEs on multi-walled CNTs (MWCNTs), single-walled CNTs (SWCNTs) and their oxidized counterparts (O-MWCNTs and O-SWCNTs), and its molecular mechanism over a wide concentration range. The sorption isotherm results revealed that the hydrophobicity of OPEs dominated their affinities on a given CNT and the pi-pi electron donor-acceptor (EDA) interaction also played an important role in the sorption of aromatic OPEs. This pi-pi EDA interaction, verified with Raman and FT-IR spectroscopy, could restrict the radial vibration of SWCNTs and affect the deformation vibration, gamma(CH) bands of OPE molecules. The OPE surface coverage on CNTs, estimated using the nonlinear Dubinin-Ashtakhov model, indicated that the oxygen-containing functional groups on CNTs could interact with water molecules by H-bonding, resulting in a decrease in effective sorption sites. In addition, FTIR analysis also confirmed the occurrence of Bronsted acid-base interactions between OPEs and surface OH groups of SWCNTs. Our results should provide mechanistic insights into the sorption mechanism of OPE contaminants on CNTs. (C) 2014 Elsevier B.V. All rights reserved.