Electrosorption of ions from aqueous solutions with carbon nanotubes and nanofibres (CNTs-CNFs) film electrodes has been demonstrated. The cost-effective, large area CNTs-CNFs film was synthesised on graphite substrate by low pressure and low temperature thermal chemical vapor deposition (CVD). Successful removal of Cu2+ from water by electrosorption of CNTs-CNFs films was achieved. The electrosorption capacity of CNTs-CNFs film electrodes was approximately 30.6~136.2 mumol/g. The ion sorption followed a Langmuir isotherm, indicating monolayer adsorption. The degradation of CNTs-CNFs electrodes for the electrosorption of Cu2+ maybe due to the electrolytic reaction occurred on the surface of the electrodes.