This paper presents an investigation into urea-to-hydrogen valorization through electro-oxidation on nickel(III). The study has dual objectives: (i) to gain a better understanding of the effects of organic compounds (other than urea) in human urine on UEO and (ii) to upscale the process to pilot-scale. Initial voltammetric studies at labscale using real human urine showed that urea adsorption on nickel(III) sites, followed by its electrooxidation, competes with molecules such as creatinine, histidine, and creatine. Notably, creatinine reduced the nickel(II) oxidation signal by up to 20 %, indicating its reaction precedence over urea. Additionally, the oxidation rate of urea by nickel(III) in urine exhibited a much lower partial order (0.1), as opposed to 0.3 in KOH solution, confirming the impact of competitive adsorption. Subsequently, UEO experiments were upscaled using a specially designed 1 L undivided tubular EC reactor operating in multi-pass mode. Potentiostatic electrolysis of a urea synthetic solution was conducted over 70 h, achieving nitrogen and carbon species mass balances of over 97 %-a milestone previously unreported at this scale. The study further examined the influence of operating parameters such as anode surface area, flow rate and applied potential on the EC process. This investigation underscored the impact of factor like reactor geometry, controlled potential and temperature on process efficiency. Parameters for optimal N 2 production, highest urea conversion rate, etc., were also defined. Finally, the electrolysis of human urine at pilot-scale unveiled new challenges distinct from those encountered with urea synthetic solutions.