We investigated the production of ammonium by the photodegradation of dissolved organic matter (DOM) in the coastal upwelling system off central Chile (36uS). The mean penetration of solar radiation (Z1%) between April 2011 and February 2012 was 9.4 m, 4.4 m and 3.2 m for Photosynthetically Active Radiation (PAR; 400–700 nm), UV-A (320–400 nm) and UV-B (280–320 nm), respectively. Ammonium photoproduction experiments were carried out using exudates of DOM obtained from cultured diatom species (Chaetoceros muelleri and Thalassiosira minuscule) as well as natural marine DOM. Diatom exudates showed net photoproduction of ammonium under exposure to UVR with a mean rate of 0.5660.4 mmol L 21 h 21 and a maximum rate of 1.49 mmol L 21 h 21. Results from natural marine DOM showed net photoproduction of ammonium under exposure to PAR+UVR ranging between 0.06 and 0.2 mmol L 21 h 21. We estimated the potential contribution of photochemical ammonium production for phytoplankton ammonium demand. Photoammonification of diatom exudates could support between 117 and 453% of spring-summer NH 4 + assimilation, while rates obtained from natural samples could contribute to 50–178% of spring-summer phytoplankton NH 4 + requirements. These results have implications for local N budgets, as photochemical ammonium production can occur year-round in the first meters of the euphotic zone that are impacted by full sunlight.