Chitin is one of the most abundant polymers in nature, with chitinous biomass often discarded as food waste and marine debris. To explore an effective way to degrade chitin, in this work, anaerobic sludge was inoculated at the anode of a two-chamber microbial fuel cell (MFC), and chitin was degraded via anaerobic respiration and fermentation. The results showed that the anaerobic sludge could degrade chitin under both the anaerobic respiration and fermentation modes, with similar degradation rates (7.10 ± 0.96 and 6.96 ± 0.23 C-mg/L·d−1). The open-circuit voltage and output current density could roughly reflect the degradation of chitin in the MFC. The maximum current density generated through the anaerobic sludge degradation of chitin via anaerobic respiration was 160 mA/m2, and the maximum power density was 26.29 mW/m2. The microbial sequencing results revealed substantially different microbial community profiles, with electroactive bacteria (EAB) flora and fermentative bacteria (Longilinea) as the main microbial groups that degraded chitin via anaerobic respiration and fermentation, respectively. Therefore, anaerobic sludge may be a good choice for the treatment of refractory biomass due to its abundant electroactive and fermentative flora.