Defect-free dielectric coatings comprised of porous polymeric matrices are prepared using nitrogen-containing polymers as pore-generating agents. The dielectric coatings are useful in a number of contexts, including the manufacture of electronic devices such as integrated circuit devices and integrated circuit packaging devices. The dielectric coatings are prepared by admixing, in a solvent, a polymeric nitrogenous porogen with a high temperature, thermosetting host polymer miscible therewith, coating a substrate surface with the admixture, heating the uncured coating to cure the host polymer and provide a vitrified, two-phase matrix, and then decomposing the porogen. The dielectric coatings so prepared have few if any defects, and depending on the amount and molecular weight of porogen used, can be prepared so as to have an exceptionally low dielectric constant on the order of 2.5 or less, preferably less than about 2.0. Integrated circuit devices and integrated circuit packaging devices manufactured so as to contain the dielectric material of the invention are provided as well.