The nanocomposite coatings were prepared on the surface of PVC substrate using spinning technique with attempts of introducing nanosized iron oxide particles with different morphology into the organic-inorganic hybrid matrices. The hybrid matrices were derived from 3-glycidoxypropyltrimethoxysilane (GLYMO) and tetraethoxysilane (TEOS) with a process of hydrolyzing and condensation. Nanosized iron oxide particles were synthesized by hydrolysis of FeCl3 solution at different pH value and different temperature. The effects of different additions on nanomechanical properties of the nanocomposite coatings were investigated using X-ray powder diffraction (XRD), transmission electron microscopy (TEM) and MTS Nano Indenter XP system. It was found that the acicular α-FeOOH and spherical α-Fe2O3 particles were synthesized, both of them dispersed homogeneously. Nanoindentation and nanoscratch behaviors of the nanoindenter system showed that both of the nanocomposite coatings reinforced the nanomechanical properties of the PVC obviously. Especially, the contribution of acicular α-FeOOH was more remarkable than the spherical α-Fe2O3.