Nanomaterials and assemblies of the aforementioned into complex architectures constitute an opportunity to design efficient and selective solutions to widespread and emerging environmental issues. The limited disposal of organic matter in modern landfills generates extremely concentrated leachates characterised by high concentrations of refractory compounds. Conventional biochemical treatment methods are unsuitable, while advanced treatment, such coagulation, reverse osmosis and ultrafiltration can be very costly and generate additional waste. Electrochemical oxidation is an established technique to efficiently mineralise a plethora of recalcitrant pollutants, however the selectivity and efficiency of the process are strongly related to the anode material. For this reason, a nanoarchitectured carbon material has been designed and synthesised to improve the capability of the anode towards the adsorption and decomposition of pollutants. Instead of simple nanostructures, intelligently engineered nanomaterials can come in handy for more efficient advanced treatment techniques. In this study, a carbon nanoarchitecture comprising boron-doped vertically aligned graphene walls (BCNWs) were grown on a boron-doped diamond (BDD) interfacial layer. The results show how the peculiar maze-like morphology and the concurrence of different carbon hybridisations resulted in a higher current exchange density. The BDD performed better for the removal of NH₄⁺ while the BCNW-only sample exhibited a faster deactivation. The BDD/BCNW nanoarchitecture resulted in an enhanced COD removal and a NH₄⁺ removal similar to that of BDD, without the intermediate production of NO₂⁻ and NO₃⁻.