The structure of the crystalline-amorphous interface of poly(R-3-hydroxybutyrate) (PHB) of different molar mass is evaluated by analysis of the rigid amorphous fraction and by analysis of the degree of reversible melting and crystallization. The rigid amorphous fraction of low-molar-mass PHB of 5 kDa is only 5-10%, and at best half of that of high-molar-mass PHB of almost 500 kDa, despite identical crystallinity. This result is paralleled by observation of distinctly larger degree of reversible melting and crystallization in PHB of high molar mass. The larger rigid amorphous fraction and higher degree of reversible melting and crystallization in PHB of high molar mass, consistently and independently, prove enhanced covalent coupling of crystals and amorphous structure, and/or de-coupling of segments of macromolecules which traverse between phases, respectively. The distinct isolation of crystals in PHB of low molar mass is discussed in terms of absence of wide loops/folds, long-chain cilia, and tie-molecules. (C) 2008 Elsevier Ltd. All rights reserved.