Patterned, amine-terminated monolayers can be fabricated from 4-nitrobenzenethiol (4-NBT) monolayers simply by irradiating under ambient conditions with visible laser after spreading Ag nanoparticles onto selected regions of the 4-NBT monolayers on Au. Air nanoparticles were adsorbed selectively onto the amine groups produced by photoreaction, and polyaniline was found to grow exclusively at the amine groups when electrochemical polymerization was conducted using the patterned substrate as the working electrode. These observations clearly support our previous contention that Ag nanoparticles can act as moderate photoelectron emitters.