A new graphene-based tetraethoxysilane-methyltrimethoxysilane sol-gel hybrid magnetic nanocomposite (FeO@G-TEOS-MTMOS) was synthesised, characterized and successfully applied in magnetic solid-phase extraction (MSPE) for simultaneous analysis of polar and non-polar organophosphorus pesticides from several water samples. The FeO@G-TEOS-MTMOS nanocomposite was characterized using Fourier transform-infrared spectroscopy, energy-dispersive X-ray spectroscopy, field emission scanning electron microscopy and X-ray diffraction. Separation, determination and quantification were achieved using gas chromatography coupled with micro electron capture detector. Adsorption capacity of the sorbent was calculated using Langmuir equation. MSPE was linear in the range 100-1000 pg mL for phosphamidon and dimethoate, and 10-100 pg mL for chlorpyrifos and diazinon, with limit of detection (S/N = 3) of 19.8, 23.7, 1.4 and 2.9 pg mL for phosphamidon, dimethoate, diazinon and chlorpyrifos, respectively. The LODs obtained is well below the maximum residual level (100 pg mL) as set by European Union for pesticides in drinking water. Acceptable precision (%RSD) was achieved for intra-day (1.3-8.7%, n = 3) and inter-day (7.6-17.8%, n = 15) analyses. FeO@G-TEOS-MTMOS showed high adsorption capacity (54.4-76.3 mg g) for the selected OPPs. No pesticide residues were detected in the water samples analysed. Excellent extraction recoveries (83-105%) were obtained for the spiked OPPs from tap, river, lake and sea water samples. The newly synthesised FeO@G-TEOS-MTMOS showed high potential as adsorbent for OPPs analysis.