Controlling the orientation and lateral ordering of the block copolymer microdomains is essential to their use as templates and scaffolds for the fabrication of nanostructured materials. In addition, a process must be robust, simple to implement, and rapid, and should not introduce disruptive processing steps that would impede their use. Here, we describe thin films of poly(styrene-b-4-vinylpyridine) (PS-b-P4VP) diblock copolymers, spin-coated from mixed solvents that show highly oriented, cylindrical microdomains with a high degree of order on a wide range of substrates, including silicon oxide, polystyrene, germanium, polyimide, and poly(butylene terephthalate). In addition, the preferential solvation of the P4VP block with an alcohol caused a surface reconstruction that resulted in the formation of a nanoporous film upon drying. The evaporation of gold onto the reconstructed films produced thermally stable and reactive ion etching resistant films.