The type of anionic initiator used to polymerize ethyl 2-cyanoacrylate was found to influence the morphology of the polymer formed via vapor phase polymerization. Depending upon the type of initiator, polymerization of ethyl 2-cyanoacrylate resulted in either the formation of neat polymer nanofibers (similar to 200 nm in diameter) or thin films. Based on the classification of anions using Hard Soft Acid Base principles, we found that harder anions favored polymer film formation while softer ones favored polymer nanofibers. Infrared (IR) spectroscopy, scanning electron microscopy (SEM) and gel permeation chromatography (GPC) were used to characterize the structure, morphology and molecular weight of the synthesized polymers, respectively. Finally, a mechanism of formation of different polymer morphologies is proposed. (C) 2008 Elsevier Ltd. All rights reserved.