This study demonstrates that PEG-assisted hydrothermal synthesis provides a convenient and eco-friendly route to fabrication of mesoporous magnetite with enhanced capacity for phosphate removal, excellent potential for magnetic separation and good reusability. Adsorption of phosphate onto 4 laboratory prepared magnetite powders was investigated in a systematic manner. Powders were synthesized in poly(ethylene) glycol-free or assisted conditions (PEGs 400 and 20,000 at varied PEG/water ratio), and characterized in terms of crystalline structure, and magnetic, morphological, textural, and acid-base properties. PEG acted as a powerful pore forming agent, the PEG/water ratio being the key factor in developing the surface area and mesoporosity of magnetite. Uptake capacity for phosphates increased with an increase in surface area and pore volume. PEG 20,000 at a ratio of 3:1 gave the best result. This mesoporous (D-max = 11 nm), nano-scale (<10 nm) magnetite was ca. 9 times more efficient than nonporous micrometric powder derived from PEG-free synthesis (Langmuir maximum capacity, q(m) = 26.2 vs. 3.0 mg g(-1)). The adsorption was pH-dependent, in accord with variations in zeta potential of magnetite. Opposite shifts of isoelectric point and point of zero charge confirmed specific adsorption of phosphates at water/magnetite interface which proceeded via replacement of surface hydroxyls and sulfates. (C) 2016 Elsevier B.V. All rights reserved.