Owing to the very low economic value of brewer's spent grains, its utilisation for biogas production is very promising. The hydrolysis of ligno-cellulose is the rate limiting step in anaerobic digestion. Enzymatic pre-treatment promotes the hydrolysis of ligno-cellulose, breaking it down to lower molecular weight substances which are ready to be utilised by the bacteria. A cheap raw multi-enzyme produced by a solid state fermentation (SSF) process is a good substitute for expensive conventional enzyme. The SSF enzyme application to spent grain has been investigated by carrying out enzymatic solubility tests, hydrolytic experiments and two-step anaerobic fermentation of spent grain. Gas chromatograph analysis was conducted to quantify fatty acids concentrations, while CH4, CO2, O-2, H-2 and H2S were measured to determine biogas quality by means of a gas analyser. DS, oDS, pH were also measured to analyse the anaerobic digestion. The result shows that enzyme application promotes the hydrolysis of ligno-cellulose, indicated by higher enzymatic solubility and fatty acid concentration in a hydrolytic bioreactor. Moreover, biogas production is also increased. The quality of the gases produced is also enhanced. Since the anaerobic digestion can be operated in a stable performance, it can also be concluded that SSF enzyme is compatible with anaerobic digestion.