A new tetraethoxysilane-polydimethylsiloxane (TEOS-PDMS) for use as sorbent of stir bar sorptive extraction (SBSE) towards two selected organophosphorus pesticides (OPPs) namely chlorpyrifos and malathion was successfully synthesized through sol–gel technology. Four different molar ratios of TEOS:PDMS (1:1, 2:1, 3:1 and 4:1) sol solutions were prepared and dipped coated onto the surface of a glass-encased stir bar. Extraction efficiency of the prepared coatings towards the two selected OPPs were compared. A number of factors have been found to greatly affect the characteristics and properties of a particular sol–gel coating. Hence, in this study, several sol–gel coating conditions have been optimized using the optimized molar ratio 3:1 TEOS:PDMS to obtain the best coating as the stationary phase for SBSE. The raw OH-TPDMS and TEOS were characterized using Fourier Transform Infrared Spectroscopy (FT-IR) and compared with spectra of the four different molar ratios of TEOS:PDMS. The FT-IR spectrum of TEOS:PDMS showed the co-polymerization between PDMS and hydrolyzed TEOS molecules demonstrating the formation of the hybrid network in the sol–gel hybrid material. Surface morphology of hybrid sol–gel TEOS-PDMS with optimized molar ratio of 3:1 TEOS:PDMS were examined using FE-SEM. The surface of the sol–gel coating seems to be rough and homogeneous. The more rough structure formed by the 3:1 molar ratio TEOS:PDMS provides enhanced surface area which in turn improved sample capacity or adsorption process.