Biogas produced from wastes, residues and energy crops has promising potential to reduce greenhouse gas emissions and to secure future energy supply. Methane is the energy-rich component of biogas, and is formed as the end product during degradation of organic material without oxygen (anaerobic). Acetate is an important intermediate in anaerobic degradation and can be converted to methane through two pathways: aceticlastic methanogenesis and syntrophic acetate oxidation (SAO). SAO is a two-step reaction, consisting of acetate oxidation to hydrogen and carbon dioxide by syntrophic acetate-oxidising bacteria (SAOB), followed by conversion of these products to methane by hydrogenotrophic methanogens. Ammonia and acetate concentration, hydraulic retention time, temperature and methanogenic population structure are operational parameters considered to influence the acetate conversion pathway. This thesis sought to increase understanding of SAO by examining syntrophic acetate oxidisers in pure culture, co-culture and methanogenic reactors. Two novel species of SAOB, Syntrophaceticus schinkii and Tepidanaerobacter acetatoxydans, were isolated and their phenotypic and phylogenetic traits were characterised. Quantitative molecular approaches were developed and applied to determine structural dynamics in the methane-producing population in a mesophilic biogas reactor during an ammonia-induced shift from aceticlastic to syntrophic acetate degradation. The abundance of SAOB increased, with a simultaneous decrease in aceticlastic methanogens. The majority of known SAOB are considered acetogens, and gradually increased ammonia concentration was shown to cause distinct shifts in the putative acetogenic population structure in mesophilic biogas reactors. However, the acetogenic bacterial abundance remained relatively stable. Bioaugmentation of syntrophic acetate-oxidising cultures did not improve process performance or support establishment of SAO as the dominant acetate degradation pathway. In conclusion, SAOB are enduring and important components of the methane-producing community in mesophilic biogas reactors with high prevailing ammonia concentrations.