The complexation between polystyrene-block-poly(acrylic acid) (PS-b-PAA) micelles and poly(ethylene glycol)-block-poly(4-vinyl pyridine) (PEG-b-P4VP) is studied, and a facile strategy is proposed to prepare core-shell-corona micellar complexes. Micellization of PS-b-PAA in ethanol forms spherical core-shell micelles with PS block as core as PAA block as shell. When PEg-b-P4VP is added into the core-shell micellar solution, the P4VP block is absorbed into the core-shell micelles to form spherical core-shell-corona micellar complexes with the PS block as core, the combined PAA/P4VP blocks as shell and the PEG block as corona. A model is suggested to characterize the core-shell-corona micellar complexes.