The formation of highly substituted carbon centers using catalysis has been a widely sought after goal, but complexes of highly substituted carbon atoms with transition metals are rare, and the factors that affect the relative stability of complexes with differentially substituted carbon atoms are poorly understood. In this study, a set of equilibrating alkyl–palladium complexes were subtly tuned to form either a primary or trisubstituted alkyl complex as the more thermodynamically favored state, depending on either the substrate or reaction conditions. An X‐ray crystal structure of the trisubstituted alkyl–palladium complex is presented and compared with the corresponding primary alkyl complex. The mechanism for rearrangement and the factors that drive the change in stability are discussed. Equilibration: A set of alkyl–palladium complexes can be subtly tuned to form the thermodynamically favored complex with either the primary or the trisubstituted alkyl complexes, depending on the substrate and the reaction conditions that are used. The mechanism for the rearrangement and the factors that drive the change in stability are discussed.