A method of forming three-dimensional structures includes forming a conductive layer on a substrate and patterning a resist layer over the conductive layer, the resist layer having contained therein a plurality of vias. An electrically conductive polymer is then electro-deposited in the vias. The electro-deposition operation is then stopped to form one or more of posts, posts having bulbous termini (i.e., mushrooms), or a layer atop the resist layer. The resist may be removed to yield the structure which may be further processed. For example, the structure may be pyrolyzed. In addition, biomolecules may also be adhered or otherwise affixed to the structure.