Core-shell nanoparticles with a polystyrene core and a hybrid copolymer shell were synthesized via emulsion polymerization of styrene and subsequent addition of gamma-methacryloxypropyltrimethoxysilane (MPS) to produce the shell by copolymerization reaction of MPS with the residual amount of styrene. The influences of pH, the amount of NIPS, and the addition mode of NIPS on the particles size, morphology, and copolymer architecture in the shell were studied using dynamic light scattering (DLS), transmission electron microscopy (TEM), gas chromatography (GC), differential scanning calorimetry (DSC), solid-state NMR, and infrared UR) spectroscopy.