Due to the low trace metals concentration in the Olive Mill Solid Waste (OMSW), a proposed strategy to improve its biomethanization is the supplementation of key metals to enhance the microorganism activity. Among essential trace metals, cobalt has been reported to have a crucial role in anaerobic degradation. This study evaluates the effect of cobalt supplementation to OMSW, focusing on the connection between fractionation of cobalt in the system and the biological response. The highest biological responses was found in a range from 0.018 to 0.035 mg/L of dissolved cobalt (0.24-0.65 mg total cobalt/L), reaching improvements up to 23% and 30% in the methane production rate and the methane yield coefficient, respectively. It was found that the dissolved cobalt fraction is more accurately related with the biological response than the total cobalt. The total cobalt is distorted by the contribution of dissolved and non-dissolved inert fractions. (C) 2016 Elsevier Ltd. All rights reserved.