The photopatterning process of self-assembled monolayer has been used as template for fabricating biomolecular microstructures. Alkanethiolates formed by the adsorption of 1-octanethiol molecules on a gold substrate were oxidized by the irradiation of deep UV light and then developed with deionized water. The resulting positive patterned substrate was immersed into a dilute ethanolic solution of 11-mercaptoundecanoic acid (11-MUDA). Cytochrome c monolayers were immobilized onto the patterned gold substrate by self-assembly technique and their electrochemical properties were investigated through the measurements of cyclic voltammetry. Also, I–V characteristics of biomolecular multilayers consisting of cytochrome c and green fluorescent protein (GFP) were studied with a scanning tunneling microscope (STM).