The synthesis of three kinds of sorbents is described. The first kind was a hydrophobic nanofiber as a specific sorbent for non-polar compounds. The second one was a hydrophilic nanofiber as a specific sorbent for polar compounds and the third one was a generic sorbent synthesized from hydrophilic and hydrophobic compounds. The functional groups were natural compounds extracted from aloin plant and gum of pine tree. The aloin/polyacrylonitrile (PAN), rosin/PAN, and aloin/rosin/PAN electrospun nanofibers were synthesized through electrospinning strategy and then characterized using field emission scanning electron microscopy and Fourier transform infrared spectroscopy. Thereafter, the synthesized sorbents were used in microextraction using the packed syringe (MEPS) method. The determination was conducted using gas chromatography with flame ionization detection (GC-FID). Under the optimum condition, the method using aloin/rosin/PAN nanofibers as a sorbent showed a good linearity in the range 1.0-250 ng mL(-1) for polycyclic aromatic hydrocarbons (PAHs) (as a model for non-polar compounds) and 1.0-200 ng mL(-1) for phenoxyacetic acid herbicides (CAPs) (as a model for polar compounds) with correlation coefficient (R-2) higher than 0.997. Limits of detections (LODs) for PAHs and CAPs were in the range 0.1-0.3 ng mL(-1) and 0.3-0.5 ng mL(-1), respectively. The intra-day (n=3) and inter-day (between 3 days) relative standard deviations (RDSs%) were in the range 6.3-12.3% for a single syringe. Finally, the MEPS-GC-FID method was applied as a simple, facile, and time and cost-effective method to analyze environmental, farm, and industrial water samples.