Fluoropolymer blends have been widely used as binders for exterior coatings because of their excellent resistance to ultra-violet (UV) radiation as well as to many corrosive chemical agents.It is known that the fluorinated component usually has a lower glass transition temperature and easily crystallizes in the final structure depending upon the blend composition and sample annealing condition.We investigated the effect of blend composition and annealing process (slow and fast cooling) on the surface morphology and microstructure a poly(vinylidene fluoride)/poly(methyl methacrylate)(PVDF/PMMA) blend before and after UV exposure.Surface and subsurface microstructures were studied by atomic force microscopy (AFM) and laser scanning confocal microscopy (LSCM).Bulk microstructure of PVDF-coatings before and after UV exposure were characterized using small angle neutron and light scattering.Higher PVDF content and a slow cooling process result in larger spherulite crystallite structure and rougher surface morphology.Significant ordering in the spherulite crystallite structure has been observed on the surface and the bulk films after UV exposure.