In this paper, we report the microelectrode array fabrication using selective wetting/dewetting of polymers on a chemical pattern which is a simple and convenient method capable of creating negative polymeric replicas using polyethylene glycol (PEG) as a clean and nontoxic sacrificial layer. The fabricated hole-patterned polypropylene film on gold demonstrated enhanced electrochemical properties. The chemical pattern is fabricated by microcontact printing using octadecanethiol (ODT) as an ink on gold substrate. When PEG is spin-cast on the chemical pattern, PEG solution, selectively dewets the ODT patterned areas and wets the remaining bare gold areas, leading to the formation of arrayed PEG dots. A negative replicas of the PEG dot array is obtained by spin-coating of polypropylene (PP) solution in hexane which preferentially interacts with the hydrophobic ODT region on the patterned gold surface. The arrayed PEG dots are not affected the during PP spin-coating step because of their intrinsic immiscibility. Consequently, the hole-patterned PP film is obtained after PEG removal. The electrochemical signal of the PP film demonstrates the negligible leakage current by high dielectric and self-healing of defects on the chemical pattern by the polymer. This method is applicable to fabrication of microelectrode arrays and possibly can be employed to fabricate a variety of functional polymeric structures, such as photomasks, arrays of biomolecules, cell arrays, and arrays of nanomaterials.