Tertiary alcohols are found as a motif in many pharmaceuticals and natural products. Elucidation of their biosynthesis is thus a good starting point for the identification of enzymes for the synthesis of chiral tertiary alcohols. To date, however, relatively few enzymatic methods for such syntheses have been established in biotechnological processes. Whereas secondary alcohols can be efficiently synthesized via the (asymmetric) reduction of ketones, a generally applicable method for the enzymatic synthesis of tertiary alcohols has been more difficult to identify. Herein, a survey of the biocatalytic methods for the synthesis of (chiral) tertiary alcohols is presented. Advantages and disadvantages of the respective methods are discussed from a synthetic point of view.