An electrostatic self-assemby (ESA) multilayer film of a diazo resin (DR) was fabricated by direct surface charge reversal. DR is first adsorbed onto the substrate via electrostatic interaction, and in the chemical activation step, the sign of the surface charge is directly reversed by converting the positively charged diazonium ion to the negatively charged diazo sulfonate ion under mild conditions. By repeating adsorption and chemical activation step, the film grows regularly layer by layer.