The investigation presented in this paper illustrates a technique for growing in-situ polymerized networks, forming scaffold-like structures usually formed by means of electrospinning. The technique of jet atomization employing electrohydrodynamics is a manifestation of electrospinning. However, we show for the first time that using this technique where individual droplets are generated, a continuous self-supporting submicrometer web-like structure can be grown whereby fragments of the structure are delivered in the droplets and polymerize on the surface of the growing structure via polycondensation. The development of these growing fibers into web structures is a direct result of the processing route together with the excellent tailor-made cross-linking nature of the resin. An operational map is generated to identify a parametric space in which the stable cone-jet mode of electrohydrodynamic atomization prevails for generating the finest droplets. A statistical analysis on the formed fibers for a given time and electrospray condition is presented to-ether with optical micrographs of the structure, which concludes the discussion in this paper.