Carbon nanofibers (CNFs) are converted into anionic current rectifiers by surface modification with amine functional groups using hydrothermal means (forming modified CNFs, with generation-3 poly (propylene imine) dendrimer, urea and boric acid). To confirm surface charge, morphological changes and carbon nanomat thickness, zeta potential analysis, transmission electron microscopy (TEM) and scanning electron microscopy (SEM), were used. When a dispersion of surface modified carbon nanofibers in DMF is drop-cast asymmetrically to form nanomats onto laser drilled microholes (5, 10, or 20 µm diameter) of poly (ethylene terephthalate) substrates and immersed into aqueous electrolyte solutions, anionic diode behaviour is observed (in contrast to pristine carbon nanofibers, which exhibit cationic diode behaviour). The effects of electrolyte type, ionic strength, and microhole diameter on ionic diode performance were investigated using cyclic voltammetry, chronoamperometry, and impedance spectroscopy. Future applications in desalination are proposed.