We report synthesis of polymer particles comprising layers with alternating high and low refractive index. We used poly(heptafluorobutyl methacrylate) as the low refractive index component and polystyrene as the high refractive index counterpart. We employed a copolymerization approach, the addition of a phase transfer catalyst (cyclodextrin), and a mixed initiator approach to produce spherical particles with a well-defined morphology. The composition and morphology of these particles were proven by DSC, XPS, NMR, and SEM. The refractive index contrast between these alternating high and low refractive index layers was ca. 0.20 +/- 0.018. This work shows a route toward synthesis of polymeric spherical dielectric resonators.