Poly(ethylene glycol dimethacrylate-co-acrylic acid) (poly(EGDMA-co-AA)) small microspheres were effectively self-assembled on poly(ethylene glycol dimethacrylate-co-4-vinylpyridine) (poly(EGDMA-co-VPy)) surfaces to form a core-corona structure with a raspberry-like polymer composite by a hydrogen interaction mechanism through an affinity complex between the carboxylic acid group and pyridine group. The control of coverage of the poly(EGDMA-co-AA) corona on the surface of poly(EGDMA-co-VPy) was studied in detail via adjustment of the nature of the mass ratio between the core and corona. The effects of the pH and solvent used on the morphology of the self-assembled core-corona polymer composites were investigated. The nature of the interaction between the core and corona polymer particles was identified as hydrogen bonding with FT-IR spectroscopy.