Ultrathin film of polyamic acid having benzene and sulfonyloxyimide moieties was prepared using the Langmuir-Blodgett (LB) technique, and then photosensitive polyimide LB film was obtained by the thermal treatment of precursor polyamic acid multilayers at 200$^{C}$ for 1 hr. The polyamic acid was synthesized by condensation polymerization under THF and pyridine cosolvent. All monomers and polymers were identified through elemental analysis, FT-IR and $^1$H-NMR spectroscopic measurements. The microarray patterning of photosensitive polyimide LB film on a gold substrate was generated with a deep UV lithography technique. The well-characterized monolayer of cytochrome c was immobilized on the microarray patterns using two different self-assembly processes. Physical and electrochemical properties of the self-assembled cytochrome c monolayer were investigated based on cyclic voltammetry and atomic force microscopy (AFM). Also, its application in bioelectronic device was examined.