Noble metal-coated PDA composite vesicles were expected to increase the effective third-order nonlinear op- tical susceptibility χ (3) (ω), due to the enhancement of the optical electric field induced by localized surface plasmon resonance. Different size (20, 50 and 80 nm) Ag colloidal nanoparticles were coated on the outer surface of polydi- acetylene (PDA) vesicles to form PDA/Ag nanocompos- ite vesicles and the size-dependent effect of Ag colloidal nanoparticles on NLO properties enhancement has been ex- plored. The explanation based on the competition of a size- dependent light-confinement effect and a size-dependent di- electric constant of Ag particles had been presented. Fur- thermore, these PDA/Ag composite vesicles were success- fully immobilized onto the solid substrate by the Langmuir- Blodgett (LB) method and their linear and nonlinear opti- cal properties were characterized, respectively. Obviously, PDA/Ag composite vesicles Langmuir-Blodgett (LB) films promoted the enhancement of the third-order NLO proper- ties.