Polyacrylonitrile nonwovens intercalated with graphene oxide (GO) sheets were prepared by a simultaneous electrospinning-spray deposition system. These hybrid nonwovens were carbonized in a two-stage process to obtain a mesostructured hybrid carbon containing carbon nanofibers (CNF) and reduced GO sheets (CNF/RGO). During the carbonization process, the CNF act as spacers between the RGO layers to prevent their compactation and restacking resulting in a three-dimensional structure. The presence of RGO increases the electrical conductivity in the CNF/RGO material. The resulting hybrid carbon is nitrogen-doped as indicated by x-ray photoelectron spectroscopy and Fourier transformed infrared spectroscopy. This N-doped porous carbon was used to prepare electrodes with improved sensitivity for the electrochemical detection of L-cysteine.