AbstractSolid‐catalyzed copolymerization reactions of ethylene and α‐olefins can produce complex mixtures generally regarded as “polyethylenes” (including linear low‐density polyethylene). The selective nature of those catalysts can lead to block‐like character in segments of polymer molecules, and these segments are sufficiently dissimilar (from a thermodynamic viewpoint) to allow for the possibility of microphase separation in the melt. Such a molecular‐level phase separation would substantially alter the melt rheology, the crystallization process, and hence the mechanical and optical properties of the resulting product. It would, in principle, be identical to those occurring in conventional well‐defined block copolymers, allowing the thermodynamic models developed for those systems to be extended to block