This letter reports a method to produce lignin and cellulose nanofibrils (CNFs) based porous core-shell carbon fibers via co-electrospinning followed by controlled carbonization. Lignin formed the shell of the fiber while CNF network formed the porous core. Polyacrylonitrile (PAN) was added to the lignin solution to increase its electrospinability. CNFs were surface acetylated and dispersed in silicon oil to obtain a homogenous dispersion for electrospinning the porous core. Hollow lignin fibers were also electrospun using glycerin as the core material. FT-IR measurements confirmed the CNF acetylation. SEM micrographs showed the core-shell and hollow fiber nanostructures before and after carbonization. The novel carbon fibers synthesized in this study exhibited increased surface area and porosity that are promising for many advanced applications. (C) 2013 Elsevier B.V. All rights reserved.