A facile approach is proposed to one-pot synthesis of two kinds of nanoparticles: a new type of PS nanobowls (a hole appearing at the bottom of nanobowl) and PS/silica hybrid multipod-like nanoparticles. The two type of nanoparticles generated together during polymerization could be separated easily by centrifugation. Furthermore, the structure of nanobowls could be easily controlled by the weight ratio of monomer/silica. In addition, we find that the multipod-like nanoparticles play important roles in hydrophobic properties. The water contact angle increased from 24.0 degrees to 143.3 degrees after coated with the multipod-like nanoparticles.