In accordance with the invention, there are surfaces exhibiting anisotropic wetting, microfluidic devices and microreactors including the surfaces and methods of controlling anisotropic wetting behavior of the surfaces. The exemplary surface can include a substrate and a plurality of rectangular shaped structures arranged to form a macroscopic pattern over the substrate, wherein the plurality of rectangular shaped structures delineate a top surface of the rectangular structures from a surface of the substrate, the rectangular shaped structures including substantially vertical walls having a height of about 100 nm to about 10 μm and wherein the shape of the macroscopic pattern, the height of the substantially vertical walls, and a surface chemistry of the top surface controls anisotropic wetting at the top surface of the rectangular structures.