This paper stated the preparation of nano-TiO2 via Sol-Gel method and modification of nano-TiO2 by coupling agent—MPS. Then Ethanol/PSt and nano-TiO2/PSt core-shell hybrid particles were prepared via miniemulsion polymerization by using the cationic surfactant Cetyl Trimethylammonium Bromide as emulsifier and Cyclohexane as co-stabilizer. These two hybrid nano-particles were added to the sizing agent—SX-5 respectively, to determine the sizing agents’ adhesive force to Terylene (T) and Terylene/Cotton (T/C) yarns respectively via roving method. The breaking strength and hairiness number of T/C yarns were determined by single yarns’ sizing method. The adhesive force of T and T/C yarns, breaking strength and hairiness number of T/C ones, showed that small size effect, high fluidity, and high surface energy caused by large specific surface area of hybrid nano-latices would make a great contribution to sizing properties.