A single synthetic route for chain-deuteriated, totally ring-deuteriated, or per-deuteriated 4-n-alkyl-4′-cyanobiphenyls has been developed. This new route gives better yields than the previously reported route for the synthesis of 4-cyano-4′-n-pentyl-d11-biphenyl and also eliminates the main “impurity” present in the final product. The synthesis of 4-cyano-4′-n-pentyl-d11-2′,3′,5′,6′-tetradeuteriobiphenyl is also reported.