Anaerobic digestion using cigarette butts, one of most littered items, was studied not only as a waste treatment, but also as an energy production method. Methane production from cigarette butts was measured through the biochemical methane potential (BMP) test and it was evaluated whether it is possible to produce electrical energy. Intact cigarettes or individual components (filter, paper, and leaf) were supplied as the sole carbon source (substrate) for the BMP test. The tendency of methane production indicated biodegradation in the order of paper, filter, and leaves; however, the filter of cigarettes was the substrate produced the highest amount of methane per total solid. The microbial community was also analyzed in each anaerobic digestion reactor, and substrate-specific microorganisms were identified, such as Proteiniphilum strain (filter) and Methanobacterium formicicum (paper). In intact cigarettes, the related microbial community became dominant over time in the order of paper, filter, and leaf. The conversion of cigarette butts to methane, a renewable energy source, can be proposed as a sustainable route for energy demand, for example, in a smoking room.