Raspberry-like hybrid nanocapsules with a hydrophobic liquid core were successfully prepared via the copolymerization of styrene, divinylbenzene (DVB), and 4-vinyl pyridine (4-VP) in Pickering-stabilized miniemulsions by using silica particles as the sole emulsifier and hexadecane (HD) as liquid template. When compared with conventional Pickering miniemulsions and Pickering suspensions, the colloidal stability of the current systems is much more sensitive to the variation of reaction parameters such as pH, size, amount of silica particles, and content of 4-VP. The systems without coagulum were only obtained in a narrow pH range at around 9.5 and by using 12 nm silica particles as emulsifier. The formation of well-defined raspberry-like capsules was confirmed by transmission electron microscopy (TEM) and high-resolution scanning electron microscopy (HRSEM). The stable attachment of silica particles on the surface of hybrid particles was verified by centrifugation and subsequent characterizations, such as Fourier transform infrared spectroscopy, TEM, and HRSEM. The influence of pH and weight content of HD, DVB, and 4-VP on the particle morphology was extensively investigated. Interestingly, the particle morphology strongly depends on the particle size. When compared with the organic surface-active surfactant, the formation of capsule morphology could be promoted by the application of silica particles taking advantage of their surface inactivity. The formation mechanisms of capsules/solid particles are discussed. (C) 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 49: 2382-2394, 2011