Electrodes constituted by nitrogen-doped reduced graphene oxide (NrGO) in combination with NiO nanostructures were fabricated by means of reactive inverse matrix assisted pulsed laser evaporation technique. The structure-composition of the electrode composites was tailored by laser-inducing chemical reactions of graphene oxide (GO) flakes with different precursor molecules (citric acid, ascorbic acid and imidazole) during GO deposition. Structural characterizations reveal the formation of wrinkles and nanoholes in the NrGO sheets, besides their coating with NiO nanostructures. Compositional studies disclose that imidazole precursor promotes the synthesis of NrGO with the largest degree of reduction and nitrogen doping (mainly with graphitic and pyridinic N). Electrochemical analyses of the obtained electrodes reveal that NiO nanostructures increase surface charge storage processes (double layer - pseudocapacitive) over diffusive ones, being the imidazole-based electrodes the ones exhibiting the best performance (up to 114 F cm(-3) at 10 mV s(-1)). Symmetric and asymmetric electro-chemical capacitors were also fabricated showing excellent robustness over 10,000 charge-discharge cycles at high specific currents.