In Korea, naked barley and tapioca are main raw materials for the production of fermentation ethyl alcohol, and one million drums bf 95% fermentation ethyl alcohol is produced per year by use of them. Stillage of alcoholic fermentation is mostly digested by methane fermentation process, and methane gas occured if methane fermentation process is recovered and mixed with fuel to decrease 25-30% for total fuel used in factories. In the anaerobic digestion process of naked barley stillage, supplement of nutrients is necessary to slove the problems caused by inhibitory materials contained if stillage and deficiency of nutrients. Therefore, the objective of this study was to examine why the anaerobic digesters using the naked barley distillery wastewater have shown the poor digestability frequently and how to control it. As the poor digestion was supposed to be occurred by the lack of iron as trace nutrient, the experiments were carried out to find out the optimum dosage and the way of addition of iron and to assess the quantitative evaluation of the type of iron in digesters. Initially, bottle test as batch digesters and lab-scaled continuous flow digesters were used in order to determine the digestion characteristics with tapioca and naked barley distillery wastewater. According to the results of batch tests, the poor digestion was caused by volatile fatty acids and could be improved by adding of calcium. The activity of the methanogenic bacteria were increased remarkably when the iron was added to the digester in the form of mixture with substrates.