AgNiO2 is a semiconductor crystallizing in the delafossite structure; it is prepared by the hydrothermal route, and the photoelectrochemical properties are studied for the first time. The TG/DSC analyses show a low stability not exceeding 290 °C before its reduction into Ag and NiO. The direct bandgap energy of the bulk material is 0.87 eV, due to the d–d transition of Ag+ linearly coordinated. AgNiO2 is chemically stable in the pH region (4–14); a flat band potential of −0.022 VRHE with p-type behavior, inferred to oxygen insertion is reported in KOH solution (10−2 M). The holes density (1.92 × 1022 cm−3) agrees with a semi-metallic behavior. Positive potentials give rise to surface oxidation of AgNiO2 in the diffusion plateau before oxygen evolution. The electrochemical oxygen insertion, investigated by chrono-amperometry, is found to be slow with a diffusion coefficient of ∼8 × 10−16 cm2 s−1. The Nyquist plot exhibits a semicircle centered below the abscissa axis, whose diameter 4200 Ω cm2 decreases down to 760 Ω cm2 under visible illumination. Such results indicate dipolar and multi-relaxation processes and confirm the existence of the optical gap. The conduction band (−0.88 VRHE) derived from Ag+: 4d orbital is more cathodic than the potential of H2O/H2 (∼−0.64 VRHE) level and hydrogen is evolved under visible irradiation. An evolution rate of 1.43 mL g−1 min−1 at pH ∼ 12.8 is obtained with a light-to-chemical energy efficiency of 2.40%.