The use of water as an oxygen and hydrogen source for the paired oxygenation and hydrogenation of organic substrates to produce valuable chemicals is of utmost importance as a means of establishing green chemical syntheses. Inspired by the active Ni3+ intermediates involved in electrocatalytic water oxidation by nickel‐based materials, we prepared NiBx as a catalyst and used water as the oxygen source for the oxygenation of various organic compounds. NiBx was further employed as both an anode and a cathode in a paired electrosynthesis cell for the respective oxygenation and hydrogenation of organic compounds, with water as both the oxygen and hydrogen source. Conversion efficiency and selectivity of ≥99 % were observed during the oxygenation of 5‐hydroxymethylfurfural to 2,5‐furandicarboxylic acid and the simultaneous hydrogenation of p‐nitrophenol to p‐aminophenol. This paired electrosynthesis cell has also been coupled to a solar cell as a stand‐alone reactor in response to sunlight.