Composite fibrous materials based on (graphene-enriched) nitrogen-doped carbon/transition metal oxides were produced by electrospinning and their physicochemical properties were thoroughly investigated by a combination of characterisation techniques. The electrochemical behaviour of the electrodes prepared with them was evaluated in view of their use in the capacitive deionisation of saline water. The morphology of the materials reminded of usnea florida lichens, wheat ears, sea sponges and noodles and depended on the transition metal (Mn, Fe, Ti or Zn). The morphology and the relative amount (14.1-22.2 wt%) of the surface nitrogen and carbon-bonded oxygen functional species, beneficial to wettability and involving pseudocapacitive processes, had strong impact on the specific capacitance (43.7-67.4 F g(-1), at 5 m V s(-1) scan rate), whereas also the specific micropore volume (0.4-5.6 mm 3 g(-1)) affected the effective areal capacitance of the electrodes (1.2-6.0 F M-2, at 5 mV s(-1)). Ion storage in the composite materials occurred via a mixed capacitive/pseudocapacitive process. Hence, increasing the content of the oxide (from 24.6 to 56.7 wt%), thanks to the fast-reversible redox reactions at or near surface it involves, partly compensated for the growing hindrance to diffusion encountered by the ions (hampered electrostatic adsorption) as the scan rate increased from 5 to 100 mV s(-1). (C) 2019 Elsevier Ltd. All rights reserved.