Layer-by-Layer self-assembly (LbL) technique is a one of well-known method for fabricating polyelectrolyte films through adsorption of anionic and cationic polymers alternately. It is possible to fabricate highly uniform and thickness controllable films at room temperature by LbL method. Moreover, we reported novel method of fabricating poly(acrylic acid) (PAA) and poly(allylamine hydrochloride) (PAH) films with metastable silver ion in previous study. Because the metastable silver ion shows redox property with reducing agent, the color change of the films is shown through reducing silver ion to nanoparticles. Here, we investigated color change of PAA/PAH multilayers with silver ion through redox reaction with ascorbic acid, which is one of reducing agent. Fabrication method of PAA/PAH multilayers with silver ion is below. Firstly, glass substrate was rinsed with pure water. After that, this substrate was immersed in positively charged PAA and negatively charged PAH alternately and dried in vacuum condition. Subsequently, this substrate was immersed in silver acetate solution and dried at room temperature. The color of fabricated LbL multilayers on the glass was changed clear to yellow after immersion in ascorbic acid solution for a one minute. Moreover, from UV-vis spectra of fabricated LbL multilayers on glass, the peak of 420 nm was observed after immersion of ascorbic acid. These results were attributed to localized surface plasmon resonance of silver nanoparticles which were generated from silver ion through redox reaction with ascorbic acid. In summary, the color of PAA/PAH multilayers with silver ion was changed after immersion of ascorbic acid because silver nanoparticles generated from silver ion through redox reaction in PAA/PAH multilayers showed localized surface plasmon resonance. This film will be widely applied to color-based sensing films for reducing agent such as ascorbic acid.