Organic-inorganic hybrid coatings containing phosphoric acid (PA) bonded to the organic-inorganic network were prepared from tetraethoxysilane (TEOS) using a sol-gel process. The effect of sol-gel phosphate-based flame retardant coating on polyacrylonitrile fabric properties (flammability, stiffness, and strength) was investigated. Sample characterization of the coated samples were investigated using differential thermal/thermogravimetric analysis (DTA/TGA), Fourier transform infrared spectroscopy (FTIR), X-ray diffractometer (XRD), and scanning electron microscopy (SEM). The results showed that hybrid coating on the polyacrylonitrile fabrics influenced fabric stiffness, strength, and flammability. And also, flammability of the coated samples after washing cycles was investigated, and the flame retardancy properties of the samples after 10 repeated washings were not completely lost.