Organic-inorganic hybrid nanoparticles have been prepared by the direct facile esterification condensation under extremely mild conditions as ambient temperature, moisture and atmospheric pressure, and the resulting composite particles are characterized by ESCA, FTIR, TEM, DLS, TGA, DSC, and XRD techniques. Results show that this facile graft method has high graft efficiency and the grafted poly(ethylene glycol) (PEG) accounts for about 55 wt% of the total silica composites. The resulting silica nanoparticles have core-shell structure with PEG on the outside and SiO2 in the core. As a result, the dispersion behavior of nanoparticles and the thermal stability of the grafted PEG are improved by the formation of covalent ester bonds between PEG and the reactive silica nanoparticles. The PEG phase, however, is disturbed by the proximity of the oxide phase of SiO2. Consequently, less crystal or faulty crystal of PEG is resulted when PEG is grafted onto the surfaces of silica nanoparticles.