The invention relates to new processes for the preparation of antireflective coatings and coated substrates, as well as articles produced by these processes. These coatings can include one or more layers made of materials which form nano-structured and/or nano-porous surfaces. The process can include applying a cross-linkable hard coat to a substrate, partially curing or cross-linking the hard coat, and then applying a second coat carried by a solvent or mixture of solvents capable of swelling the partially cured hard coat. The second coat is then cross-linked and grafted to the hard coat to produce a durable coated substrate with antireflective properties.