The hybrid miniemulsion polymerization of acrylates in the presence of alkyd resin was carried out. The polymers obtained were characterized via gel permeation chromatography, carbon nuclear magnetic resonance, and differential scanning calorimetry analysis and selective extraction; they had a quite broad molecular weight distribution. The double bonds that served as grafting sites of the alkyd onto the polyacrylate were mostly those near acid groups. The final product contained some free alkyd and some free polyacrylate, but the predominant form was poly(acrylate-graft-alkyd). This confirmed that monomer droplet nucleation is the predominant nucleation mechanism for this hybrid miniemulsion polymerization system.