Terminal restriction fragment length polymorphism (T-RFLP) was applied to study the changes in the composition of the methanogens of biogas-producing microbial communities on adaptation to protein-rich monosubstrates such as casein and blood. Specially developed laboratory scale (5-L) continuously stirred tank reactors have been developed and used in these experiments. Sequencing of the appropriate T-RF fragments selected from a methanogen-specific (mcrA gene-based) library revealed that the methanogens responded to the unconventional substrates by changing the community structure. T-RFLP of the 16S rDNA gene confirmed the findings.