Chlorinated aliphatic hydrocarbons are widely used as solvents and as intermediates in chemical synthesis, so they can be found in industrial wastewaters and released to the environment where they became a serious health risk due to their toxic properties and high chemical stability. Most of these compounds are xenobiotic and recalcitrant to biodegradation. In this article we report the effect of different co-substrates in the 1,1,1,2-tetrachloroethane (1,1,1,2-TeCA) degradation by anaerobic granular sludge, and its degradative pathway. Our results show that this compound is easy and rapidly biodegradable under methanogenic conditions, even in the absence of external electron donors. 1,1,1,2-TeCA is equimolecularly degraded to 1,1-dichloroethene (1,1-DCE) by reductive dichloroelimination. 1,1-DCE is only completely biodegraded in the presence of lactic acid as co-substrate. Although 1,1,1,2-TeCA can be apparently removed by autoclaved granular sludge, the compound is not transformed but retained inside the granules. The primary biodegradation of 1,1,1,2-TeCE to 1,1-DCE is a biotic process mediated by anaerobic bacteria.