In this work, three distinct heteroepitaxial single-crystal boron-doped diamond (SC-BDD) electrodes were fabricated and subjected to detailed surface analysis and electrochemical characterization. Specifically, the heteroepitaxy approach allowed to synthesize large-area (1 cm²) and heavily-doped (100)-oriented SC-BDD electrodes. Their single-crystal nature and crystal orientation were confirmed by X-ray diffraction, while scanning electron and atomic force microscopies revealed marked variations in surface morphology resulting from their growth on respective on-axis and off-axis substrates. Further, absence of sp² impurities along with heavy boron doping (>10²¹ cm⁻³) was demonstrated by Raman spectroscopy and Mott-Schottky analysis, respectively. Cyclic voltammetry (CV) in a 0.1 M KNO₃ solution revealed wide potential windows (∼3.3 V) and low double-layer capacitance (<4 μF cm⁻²) of the SC-BDD electrodes. Their highly conductive, ‘metal-like’ nature was confirmed by CV with [Ru(NH₃)₆]^3+/2+ probe manifesting near-reversible redox response with ΔE_p approaching 0.059 V. The same probe was used to record scanning electrochemical micrographs, which clearly demonstrated homogeneously distributed electrochemical activity of the heteroepitaxial SC-BDD electrodes. Minor differences in their electrochemical performance, presumably resulting from the somewhat different morphological features, were only unveiled during CV with surface sensitive compounds [Fe(CN)₆]^3−/4− and dopamine. The latter was also used to show the possibility of applying herein developed heteroepitaxial SC-BDD electrodes for electrochemical sensing, whereas experiments with anthraquinone-2,6-disulfonate revealed their enhanced resistance to fouling. All in all, heteroepitaxial SC-BDD represents a highly attractive electrode material which can, owing to the fabrication strategy, easily overcome size limitation, currently preventing broader use of single crystal diamond electrodes in electrochemical applications.