A novel route to hyperbranched polystyrene (HPS) from 4-vinylbenzyl N, N-diethyldithiocarbamate (VBDC) as an inimer by one-pot photopolymerization is presented. This polymerization proceeded by the self-addition living radical mechanism. Statistical branched HPS was prepared by living radical copolymerization of VBDC with styrene under UV irradiation. Hyperbranched poly(ethyl methacrylate) (HPEM) was also prepared by self-addition living radical polymerization from 2-(N, N-diethyldithiocarbamyl) ethyl methacrylate (DCEM). These hyperbranched polymers behaved as hard spheres even in a good solvent and formed a single molecule in solution. Moreover, we have established more complex molecular architectures using inimers as starting materials such as star, star-block, alternating hyperbranched, star-hyperbranched copolymers, and reactive microspheres. For application of functional nano-materials, we demonstrated a new class of holographic recording and structural color films constructed by hyperbranched polymers and reactive microspheres, respectively.