The challenge of doping synthetic diamond with phosphorus stems from the atomic size mismatch between phosphorus and carbon atoms, which previously hindered achieving high phosphorus doping levels. This limitation delayed the exploration of phosphorus-doped diamond (PDD) in electrochemical applications, where it holds potential as a novel and appealing electrode material because PDD uniquely combines diamond's exceptional properties with phosphorus atoms inducing n-type conductivity. In this study, heavily doped PDD electrodes were successfully developed using chemical vapour deposition, followed by comprehensive microstructural and electrochemical characterisations. The influence of phosphorus doping, manipulated via high phosphine gas concentration or time-dependant precursor gas flow control, on the PDD properties was thoroughly examined. PDD layers grown at higher phosphine concentrations demonstrated enhanced phosphorus incorporation, leading to a higher prevalence of fine nano-crystalline diamond grains and non-diamond carbon components, while also slowing the growth rate. Notably, a distinct PDD sample produced under dynamic gas flow with lower phosphine concentration revealed larger grain sizes, increased effective deposition rate, and improved phosphorus levels compared to its counterpart synthesized under static conditions. Cyclic voltammetry in a 1 mol L⁻¹ KCl solution revealed a low double-layer capacitance (<11 µF cm⁻²) in all as-grown PDD electrodes. However, significant differences between the samples emerged during the experiments conducted with redox probes [Ru(NH₃)₆]^3+/2+ and [Fe(CN)₆]^3−/4−. Particularly, higher phosphorus content promoted well-developed voltammograms, significantly reduced peak-to-peak separation values, faster electron transfer rates, and increased peak currents. Furthermore, the possibility of using heavily P-doped diamond electrodes for the detection of two organic analytes, dopamine and ascorbic acid, was successfully manifested. All in all, the as-grown, highly P-doped diamond electrodes proved their ability, first time ever, to record well-defined signals of both inorganic redox probes and complex organic compounds, unravelling their potential in electroanalysis and sensor development and broadening the scope of PDD utilisation.