In most cases, enantiomers of chiral compounds behave differently in biochemical processes. Therefore, the effects and the environmental fate of the enantiomers of chiral pollutants need to be investigated separately. In this review, the different fates of the enantiomers of chiral phenoxyalkanoic acid herbicides, acetamides, organochlorines, and linear alkylbenzenesulfonates are discussed. The focus lies on biological degradation, which may be enantioselective, in contrast to non-biotic conversions. The data show that it is difficult to predict which enantiomer may be enriched and that accumulation of an enantiomer is dependent on the environmental system, the species, and the organ. Racemization and enantiomerization processes occur and make interpretation of the data even more complex. Enantioselective degradation implies that the enzymes involved in the conversion of such compounds are able to differentiate between the enantiomers. "Enzyme pairs" have evolved which exhibit almost identical overall folding. Only subtle differences in their active site determine their enantioselectivities. At the other extreme, there are examples of non-homologous "enzyme pairs" that have developed through convergent evolution to enantioselectively turn over the enantiomers of a chiral compound. For a better understanding of enantioselective reactions, more detailed studies of enzymes involved in enantioselective degradation need to be performed.