In most natural ecosystems heterotrophic microorganisms encounter complex mixtures of carbon sources, each of which is present at a concentration of few micrograms per litre. This study examined the biotreatability and kinetics of an upflow anaerobic sludge blanket (UASB) reactor to complex mixtures of chlorophenols encountered in environmental conditions using on-line and off-line experimental studies. Results indicate that (1) steady-state concentration was quite lower (98.3 mg L(-1)) with complex mixture of chlorophenols than steady-state concentration achieved when only 2.4 dichlorophenol (124 mg L(-1)) was studied alone on the same reactor; (2) that toxic effects of chlorophenols increase with increasing concentrations of toxicant. (Onset of the inhibitory effect occurred at a lower concentration in multi-substrate than in single substrate utilization): (3) addition of alternative utilizable substrate can mitigate toxic effects and enhance degradation; (4) the relative concentration of substrate was critical in determining utilization patterns. HPLC analysis of off-line experimental samples resulted in a steady-state treatment efficiency of 68% for COD, 36% for 2-chlorophenol, 40.5% for 4-chlorophenol, 70.7% for 2,4-dichlorophenol, 53.2% for 2,4,6-trichlorophenol and 42% for pentachlorophenol in presence of glucose. Kinetic constant in terms of Vmax and Ks were determined. Ks for the five chlorophenols ranged between 0.016 and 0.117 kg m(-3) day(-1) while Vmax range between 0.056 and 0.244 kg m(-3) day(-1).