ABSTRACT Precision polyethylenes with 21‐carbon alkyl branches precisely spaced on every either 15th or 19th carbon along the polymer backbone lead to the formation of two kinds of lamellae, yielding different thicknesses during the crystallization process. Thinner lamellae originate from side‐chain crystallization, whereas thicker lamellae are formed by cocrystallization of the branch and the main chain. Side‐chain crystallization (separate from main chain crystallization) is favored when the branch is placed on every 15th carbon. Cocrystallization (side chain with main chain) is favored with the branch on every 19th carbon. Both form stable hexagonal crystal units. A branch spacing separation of just four carbons along the main chain makes a remarkable difference in crystallization behavior. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55 , 3090–3096