The formation of novel high aspect ratio nanofibers from polyesteramides based on epsilon-caprolactam and epsilon-caprolactone is reported. Nanofibers were prepared by the electrospinning method from polymer solution. Scanning electron microscopy images of nanofiber layers revealed that the diameter of fibers depended on the nature of the solvent or the mixture of solvents used and especially on the composition of polyesteramides.