Fermentative degradation of hydroquinone, catechol, and phenol was demonstrated with nearly‐homogeneous mixed methanogenic cultures obtained from freshwater sediments and sewage sludge by enrichment with the respective phenolic substrates. Gram‐negative short rods predominated in these cultures, together with hydrogen‐ and acetate‐utilizing methanogens. Acetate and methane were the only degradation products. Bacteria enriched with hydroquinone or catechol also degraded phenol and p‐hydroxy‐benzoate, but not resorcinol or resorcylic acids. Phenol was formed as an intermediate during catechol and hydroquinone degradation, indicating that reductive dehydroxylation was the primary event in degradation of these substrates. Inhibition experiments with bromoethanesulfonate and acetylene indicated that catechol, hydroquinone, and phenol degradation depended on a syntrophic co‐operation of fermenting bacteria and hydrogen‐oxidizing methanogens.