Electrochemical reaction of Ag+ in the interlayer of various layered oxides was investigated in this study. Intercalation of Ag+ into the interlayer of layered oxides was carried out with layer-by-layer self assembly (LBL) method. Film deposition with LBL method was monitored by UV–vis spectra. Ag+ intercalated layered oxide films showed very unique characteristics when compared to other similar Ag+ exchanged zeolite and clay electrodes. First of all, the peaks are very sharp and clear, which shows that the redox reaction in the interlayer is fast. In addition, there is an energy gap between the onset potentials of redox reactions, which is different from the behavior of other electrodes. The formation of the energy gap was assigned to the energy barrier in the host layer. Furthermore, pH and scan rate controlled experiments showed that the reaction has diffusion controlled mechanism and diffusion of H+ or K+ into interlayer is believed to be contributing to the redox reaction indirectly. The slope of I p versus ν 1/2 curves shows that redox reaction is reversible. The unique electrochemical behavior of the Ag+ intercalated layered oxide thin films may lead into the design of new nanocells using the potential energy difference between two different redox couple.