Municipal sewage sludge was immobilized to produce hydrogen gas under anaerobic conditions. Cell immobilization was essentially achieved by gel entrapment approaches, which were physically or chemically modified by addition of activated carbon (AC), polyurethane (PU), and acrylic latex plus silicone (ALSC). The performance of hydrogen fermentation with a variety of immobilized-cell systems was assessed to identify the optimal type of immobilized cells for practical uses. With sucrose as the limiting carbon source, hydrogen production was more efficient with the immobilized-cell system than with the suspended-cell system, and in both cases the predominant soluble metabolites were butyric acid and acetic acid. Addition of activated carbon into alginate gel (denoted as CA/AC cells) enhanced the hydrogen production rate (v(H2)) and substrate-based yield (Y((H2)/sucrose)) by 70% and 52%, respectively, over the conventional alginate-immobilized cells. Further supplementation of polyurethane or acrylic latex/silicone increased the mechanical strength and operation stability of the immobilized cells but caused a decrease in the hydrogen production rate. Kinetic studies show that the dependence of specific hydrogen production rates on the concentration of limiting substrate (sucrose) can be described by Michaelis-Menten model with good agreement. The kinetic analysis suggests that CA/AC cells may contain higher concentration of active biocatalysts for hydrogen production, while PU and ALSC cells had better affinity to the substrate. Acclimation of the immobilized cells led to a remarkable enhancement in v(H2) with a 25-fold increase for CA/AC and ca. 10- to 15-fold increases for PU and ALSC cells. However, the ALSC cells were found to have better durability than PU and CA/AC cells as they allowed stable hydrogen production for over 24 repeated runs.