The nanofibrous polycaprolactam (polyamide 6 (PA6)) incorporated with manganese oxide (MnO) nanoparticles was fabricated by electrospinning and used as a new fiber coating for headspace-solid phase microextraction (HS-SPME) of the selected phthalate esters (PEs) in water samples prior to GC-mu ECD. The adsorbent was fully characterized using scanning electron microscopy (SEM), Fourier transform-infrared (FT-IR) spectroscopy and thermogravimetric analysis (TGA). The main parameters that affect the HS-SPME efficiency such as extraction temperature, ionic strength, extraction and desorption times were investigated. The analytical figures of merit were obtained under the optimized conditions as follows: linear dynamic range (LDR), 0.500-5.00 x 10(2) ng mL(-1); relative standard deviations (RSDs, n = 3), 1.86-10.9%; limits of detection (LODs), 0.0400-0.193 ng mL(-1). The method was applied for determination of the target analytes in river water, bottled water, mineral water and soda samples and the relative recoveries were obtained between 90.3 and 107%. (C) 2017 Elsevier Ltd. All rights reserved.