The performance of capacitive deionization (CDI) mainly relies on the ion electrosorption capability. Here, we introduce a kind of free-standing, highly porous carbon nanofiber (CNF) networks with enhanced desalination capacity. The CNF networks were easily prepared by electrospinning of phenolic resin (PhR) precursor followed by one-step carbonization step. The as-obtained PhR-based CNF networks exhibited characteristics of high flexibility, conductivity and specific surface area (SSA) along with favorable porosity, and hence demonstrated enhanced desalination capacity. When used as CDI electrodes, the PhR-based CNF networks have demonstrated a desalination capacity of 50.1 mg g(-1) toward 2000 mg L-1 brackish water at 1.2 V, much better than most reported data thus far. More importantly, easy recovery and good reproducibility could be obtained for such electrodes. Therefore, construction of PhR-based CNF network electrodes offers remarkable opportunities for improving CDI capabilities and reliability given its simplicity, easy operation, and high performance. (C) 2014 Elsevier B.V. All rights reserved.