The behavior of electrospun polyvinyl alcohol (PVA) and polyethylene oxide (PEO) nanofibers embedded with urea is studied as a function of various process parameters. Our results show that three‐dimensional nanofiber networks can be obtained when high concentrations of urea in the solution are used during electrospinning. The nanofibers are characterized using both scanning electron microscope (SEM) and Fourier transform infrared spectroscopy (FTIR). The stability of the nanofiber as a function of electric field has also been studied. The successful formation of three‐dimensional nanofiber networks can open new trends toward applications in fertilizers containing nanofibers in the nanoagricultural field. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 39840.