Raspberry-like aggregates containing secondary nanospheres were studied. the formation of raspberry-like aggregates was due to complexation between core-shell microspheres and core-corona-micelles. The core-shell microspheres were synthesized with soap-free polmerization of styrene and methyl acrylic acid, which included carboxyl groups in the periphery. The micelles were self-assembled by polystyrene-block-poly(4-vinylpyridine), which contained pyridine groups in the corona. The driven force to form raspberry-like aggregates was due to the affinity between the carboxyl and pyridine groups. The morphology of the raspberry-like aggregates could be tuned by changing the ratio of the microspheres to micelles. IR measurements suggested that the raspberry-like aggregates were like zwitterions.