Multifunctional patterned polymeric surfaces are of significant importance to numerous surface-based researches. We demonstrated that a commercial polymer of polyethylenimine (PEI) with rich amino groups can be used as a versatile ink for the direct fabrication of patterned PEI surfaces via a supramolecular interaction between amino groups in PEI and –OH on a silicon wafer induced by microcontact printing (μCP). The thicknesses and shapes of the formed PEI surfaces can be finely tuned by changing the molecular weight and/or the concentration of PEI. The obtained patterned polymeric surfaces could be amplified further to grow other polymer brushes, or explored as novel surface-enhanced Raman scattering (SERS) active materials by electrostatic adsorption with negatively charged gold nanoparticles (AuNPs).