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The utilization of wood vinegar, a by-product of biomass pyrolysis, treated as wastes of agriculture and forest, has been attracting increasing interests all over the world. The anaerobic initial adsorption and degradation of wood vinegar to produce methane was investigated by using the activated sludge. The results indicated that the pseudoequilibrium of the anaerobic initial adsorption could be established in 10min and the rate of degradation was 15.6% while the physical adsorption played a significant role. Physical and biological adsorption was interacted after 10min. Accompanied by the acidification, the content of acetic acid and propionic acid were increased resulted in the pH value decreased. The style of organic matter adsorbed and degraded was mainly on phenolic compounds detected by GC—MS technique. The adsorption can be well described by the Freundlich equilibrium model. Methane analyzed by GC technique was increased with the increasing initial volume fraction of wood vinegar. The way of anaerobic adsorption and degradation on the activated sludge is the new path to treat the wood vinegar.