Anew spicule-like cellulose nanostructure is prepared from electrospun cellulose nanofibers using a onepot bifunctional catalysis strategy namely hydrolytic hydrogenation. The electrospun cellulose nanofibers or cellulose film was treated in presence of catalyst consisting of an alkali and a metal to produce celluloses with structures like nanospicules, nanoflowers or nanorods, respectively. This work highlights the promising combination of electrospinning and hydrolysis/hydrogenation for facile production of hierarchical cellulose nanostructures such as nanospicules and nanorods. (C) 2014 Elsevier Ltd. All rights reserved.