Olive oil is one excellence of the Italian food industry: around 300 kt yr−1 are produced, creating roughly the same amount of olive mill wastewater (OMW) to be disposed of. The present work describes a process to exploit OMW by converting its organic compounds to valuable gaseous biofuel. A sample OMW was characterized (COD, TOC, solids, and polyphenols) and submitted to membrane filtration tests to concentrate the organic compounds. Based on the results of the experiments, a treatment process was outlined: the retentate streams from microfiltration and ultrafiltration steps were fed to a cracking and a steam reforming reactor, respectively; the obtained syngas streams were then mixed and sent to a methanation reactor. The process was simulated with Aspen Plus (AspenTech©) software, assessing operating conditions and streams compositions: the final biofuel is around 81 mol.% methane, 4 mol.% hydrogen, and 11 mol.% carbon dioxide. The permeate stream cannot be directly disposed of, but both its amount and its polluting charge are greatly reduced. The heat needed by the process, mainly due to the endothermic reactions, can be obtained by burning an amount of olive pomaces, roughly corresponding to one-third of the amount left by olive treatments giving rise to the processed OMW feed.