The environmental contaminants phthalic acid esters (PAEs) were determined by aromatic hydroxylation fluorimetry combined with heterogeneous photo-Fenton process in the presence of vermiculite supported BiFeO3 (VMT-BiFeO3). In strong alkaline solution, PAEs were hydrolyzed into phthalates with no fluorescence, which then reacted with hydroxyl free radicals produced in photo-Fenton process catalyzed by VMT-BiFeO3 to form the fluorescent hydroxyl phthalates. The fluorescence intensity was proportional to the concentration of PAEs with the maximum excitation and emission wavelength of 300 nm and 417 nm, respectively. A good linear relationship can be obtained in the range of 3.8 x 10(-7) to 4.8 x 10(-5) mol L-1 for DEP with correlation coefficient of 0.9997, and the sensitivity of the method was high with detection limit of 5.43 x 10(-8) mol L-1. The method has been successfully applied to determine total PAEs in airborne particulates with satisfactory results. (C) 2016 Elsevier B.V. All rights reserved.