Poly(ε-caprolactone)-graphene oxide (PCL-GO) honeycomb-patterned films were successfully fabricated by breath figure method for the first time by the simple blending of individual components in a water miscible solvent, tetrahydrofuran. PCL-GO films were reduced using sodium borohydride to obtain PCL-reduced graphene oxide (PCL-rGO) films. The films were characterized by their color, thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS). TGA result shows the improvement of the thermal properties of PCL by the incorporation of GO. The SEM image shows the formation of monodispersed porous honeycomb-patterned PCL-GO films, and these patterns are retained after the reduction of GO to PCL-rGO without any wreckage. The reduction of GO to rGO was confirmed from the color of the films and from the XPS analysis. The present methodology is expected to widen the use of breath figure technique to achieve a wide variety of functionalized films by simple blending using water miscible solvents, which would otherwise not be possible using water immiscible solvents.