Electrospinning of biologically significant polymers (natural and synthetic polypeptides) has increased since electrospun membranes were identified as candidates for tissue engineering constructs. These materials have a specific secondary structure, which influences their properties. The effect of electrospinning on the secondary structure of nylon-6 and nylon-12 is examined using Raman spectroscopy in order to identify and quantify any conformational changes that occur due to processing. Nylon-6 and nylon-12 were chosen because they possess a specific chain conformation and have a backbone chemical structure similar to the amino acid sequence in polypeptides. Results indicate that a change in the chain conformation due to electrospinning occurs, implying that a high stress is induced on the electrospinning jet as the fibers are being formed, and this stress alters the chain conformation of the nylon backbone.