The ongoing challenge of water pollution by contaminants of emerging concern calls for more effective wastewater treatment to prevent harmful side effects to the environment and human health. To this end, this study explored for the first time the implementation of single-crystal boron-doped diamond (BDD) anodes in electrochemical wastewater treatment, which stand out from the conventional polycrystalline BDD morphologies widely reported in the literature. The single-crystal BDD presented a pure diamond (sp³) content, whereas the three other investigated polycrystalline BDD electrodes displayed various properties in terms of boron doping, sp³/sp² content, microstructure, and roughness. The effects of other process conditions, such as applied current density and anolyte concentration, were simultaneously investigated using carbamazepine (CBZ) as a representative target pollutant. The Taguchi method was applied to elucidate the optimal operating conditions that maximised either (i) the CBZ degradation rate constant (enhanced through hydroxyl radicals (^•OH)) or (ii) the proportion of sulfate radicals (SO₄^•−) with respect to ^•OH. The results showed that the single-crystal BDD significantly promoted ^•OH formation but also that the interactions between boron doping, current density and anolyte concentration determined the underlying degradation mechanisms. Therefore, this study demonstrated that characterising the BDD material and understanding its interactions with other process operating conditions prior to degradation experiments is a crucial step to attain the optimisation of any wastewater treatment application.