The deposition behavior and photoelectric response characteristics of chlorophyll a (Chl a) monolayers and multilayers were investigated under various film fabrication conditions. Chl a LB films were deposited onto quartz and pretreated ITO glass substrates under several fabrication conditions, including surface pressure and number of layers. The absorption spectra of Chl a in a solution state and solid-like state (LB films) were fairly consistent with each other, and two absorption peaks were found at 678 and 438 nm, respectively. The prepared Chl a LB films were set into an electrochemistry cell equipped with a Pt plate as the counter electrode, and the photoelectric response characteristics were obtained and analyzed relative to the light illumination. By considering the resulting photocurrents, the optimal fabrication conditions for Chl a LB films were determined as 20 mN/m of surface pressure and 20 layers. The action spectrum of the Chl a LB films was obtained in the visible region, and was found to be in good agreement with the absorption spectrum. The possible application of the proposed system as a constituent of an artificial color recognition device was suggested based on combining with the photoelectric conversion property of another light-sensitive biological pigment.