Transition/alkaline earth metal oxide composite nanofibers (TAMNs) Ca3Co4O9 and MgCo3O5 as a new class of oxide materials for hydrogen evolution were successfully fabricated by electrospinning followed by calcinations under mild condition, and characterized by scanning electron microscopy (SEM), thermogravimetric analysis (TGA), high resolution transmission electron microscope (HR-TEM), Raman spectroscopy, X-ray powder diffraction (XRD) and electrochemical method. The layered Ca3Co4O9 and MgCo3O5 nanofibers (NFs) have promising capabilities as electrocatalyst for hydrogen evolution, exhibit low Tafel slope of 76 and 98 mV/decade for hydrogen evolution reaction (HER). The affordability and electrocatalytic properties have endowed TAMNs as a potential replacement for precious metal in electrocatalytic applications. (C) 2016 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.