Sludge morphology considerably affects the mechanism underlying microbial anaerobic degradation of phenol. Here, we assessed the phenol degradation rate, specific methanogenic activity, electron transport activity, coenzyme F₄₂₀ concentration, and microbial community structure of five phenol-degrading sludge of varying particle sizes (i.e., < 20, 20–50, 50–100, 100–200, and > 200 μm). The results indicated an increase in phenol degradation rate and microbial community structure that distinctly correlated with an increase in sludge particle size. Although the sludge with the smallest particle size (< 20 μm) showed the lowest phenol degradation rate (9.3 mg COD·gVSS⁻¹ day⁻¹), its methanogenic activity with propionic acid, butyric acid, and H₂/CO₂ as substrates was the best, and the concentration of coenzyme F₄₂₀ was the highest. The small particle size sludge did not contain abundant syntrophic bacteria or hydrogenotrophic methanogens, but contained abundant acetoclastic methanogens. Moreover, the floc sizes of the different sludge varied in important phenol-degrading bacteria and archaea, which may dominate the synergistic mechanism. This study provides a new perspective on the role of sludge floc size on the anaerobic digestion of phenol.