Structured thermoset thermoplastic hybrid nanoparticles and composite coatings were successfully synthesized through a novel one-pot approach. Both the polyaddition of epoxy curing and the free radical polymerization of various vinyl monomers were performed in sequence in miniemulsion droplets. Benefiting from the precise control of the compatibility between thermoset phase (epoxy monomer/amine curing agent) and vinyl phase (vinyl monomers/polymers), colloidally stable, core shell structured thermoset thermoplastic hybrid nanoparticles between 100 and 200 nm were obtained through chemically induced phase separation. The influence of the compositions on the colloidal stability and morphology of the final hybrid latexes and films was studied in detail: Meanwhile, the mechanical properties of thermoset thermoplastic coatings and corresponding thermoplastic coatings were investigated. It is found that the thermoset thermoplastic composite coatings showed significantly improved film properties in terms of hardness compared to the analogous thermoplastic coatings. Furthermore the thermoset thermoplastic hybrid films were highly transparent even with 33 wt% of epoxy thermoset domains embedded. (C) 2014 Published by Elsevier Ltd.