In this work, polystyrene-based oil-in-water Pickering emulsion stabilized by nanocrystalline cellulose (NCC) was formulated. The NCC was prepared by sulfuric-acid-catalyzed hydrolysis of microcrystalline cellulose, with a yield of 60% and an average particle size of about 152.9 nm. When the content of NCC was 5 g/L, the surface tension was 54.58 mN/m, and stable styrene-based Pickering emulsion was prepared using NCC as the stabilizer. The presence of NCC particles in the emulsion system resulted in high resistance against creaming. Due to improved stability, the conversion efficiency of styrene was higher in the polymerization process of the styrene-based Pickering emulsion.