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A mathematical model was developed to describe phenol degradation in an anaerobic fixed‐biofilm process. The model incorporates the mechanisms of diffusive mass transport and Monod kinetics. The model was solved using a combination of the orthogonal collocation method and Gear's method. A pilot‐scale column reactor was used to verify the model. Batch kinetic tests were conducted independently to determine the biokinetic parameters used in the model, while shear loss and initial thickness of biofilm were assumed so that the model simulated the substrate concentration results well. The removal efficiency for phenol was approximately 98.5% at a steady‐state condition. The model accurately described the effluent substrate concentrations and the sequence of biodegradation in the reactor. The model simulations are in agreement with the experimental results. The approaches presented in this paper could be used to design full‐scale anaerobic fixed‐biofilm reactor systems for the biodegradation of phenolic substrates.

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