Pharmaceuticals, agrochemicals, fragrances, fine chemicals, and natural product chemistry all rely on the preparation of enantiomerically enriched compounds. The palladium-catalyzed asymmetric allylic substitution, which allows for the enantioselective formation of carbon-carbon and carbon-heteroatom bonds, is a potential synthetic tool for preparing these compounds. To date, most of the successful ligands reported for the Pd-catalyzed allylic substitution reactions have used three main design strategies. The first, developed by Hayashi and co-workers, used a secondary interaction of the nucleophile with a side chain of the ligand to direct the approach of the nucleophile to one of the allylic terminal carbon atoms. The second increased the ligand's bite angle in order to create a chiral cavity in which the allyl system is perfectly embedded. To discriminate electronically between the two allylic terminal carbon atoms, the third strategy employed heterodonor ligands. Although many chiral ligands have been successfully applied in the substitution of several disubstituted substrates, problems generally remain with both substrate specificity and reaction rates using these methods. Other substrates, such as those that are monosubstituted, will require more active and more regio- and enantioselective Pd-catalysts. Overcoming these limitations requires research toward the development of new ligands. This Account discusses the application of homo- and heterodonor biaryl-containing phosphites as new, versatile, and highly effective ligands in the Pd-catalyzed asymmetric allylic substitution of several substrate types. We and others recently demonstrated that the inclusion of biarylphosphite moieties in ligand design is highly advantageous. In these systems, the catalyst's substrate specificity decreases because the chiral pocket created (the chiral cavity with the embedded allyl ligand) is flexible enough to allow the perfect coordination of hindered and unhindered substrates. Reaction rates with these ligands increase because of the larger pi-acceptor ability of these moieties. The ability of the phosphite moiety to accept pi-electrons and enhance the S(N)1 character of the nucleophilic attack increases the regioselectivity of the reactions toward the desired branched isomer in monosubstituted linear substrates. Finally, the easy synthesis of biaryl phosphites from readily available alcohols allows for simple ligand tuning as well as systematic modifications of several important ligand parameters. Taking advantage of these features, we and others have designed highly adaptative biaryl-phosphite-containing ligands for asymmetric Pd-allylic substitution reactions. In this context, several diphosphites, phosphite-oxazolines, and phosphite-phosphoroamidites have recently emerged as extremely effective ligands for this process. Using a broad range of mono- and disubstituted hindered and unhindered linear and cyclic substrates, we have obtained high activities (turnover frequencies up to 22,000 mol substrate x (mol Pd x h)(-1)) unprecedented in the literature along with excellent regio- (up to 99%) and enantioselectivitites (up to >99%) at low catalyst loadings (turnover numbers up to 10,000 mol substrate x (mol Pd x h)(-1)). Appropriate ligand tuning allows access to both enantiomers of the substitution products.