Solid-state NMR techniques have been employed to investigate the domain structure and mobility of the bacterial biopolymeric metabolites such as poly(3-hydroxybutyrate) (PHB) and its copolymers poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) containing 2.7 mol% (PHBV2.7) and 6.5 mol% (PHBV6.5) 3-hydroxyvalerate. Both single-pulse excitation with magic-angle spinning (SPEMAS) and crosspolarization magic-angle spinning (CPMAS) C-13 NMR results showed that these biopolymers were composed of amorphous and crystalline regions having distinct molecular dynamics. Under magic-angle spinning, H-1 T-1P, and C-13 T-1, showed two processes for each carbon. Proton relaxation-induced spectral editing (PRISE) techniques allowed the neat separation of the C-13 resonances in the crystalline regions from those in the amorphous ones. The proton spin-lattice relaxation time in the tilted rotating frame, H-1 T-I(p)T, measured using the Lee-Goldburg sequence with frequency modulation (LGFM) as the spin-locking scheme, was also double exponential and significantly longer than H-1 T-1p. The difference between H TT for the amorphous and crystalline domains was greater than that of 1H T-1P. Our results showed that the H T-1(p)T differences could be exploited in LGFM-CPMAS experiments to separate the signals from two distinct regions. 1H spin-diffusion results showed that the domain size of the mobile components in PHB, PHBV2.7 and PHBV6.5 were about 13, 24 and 36 nm whereas the ordered domain sizes were smaller than 76, 65 and 55 nm, respectively. The results indicated that the introduction of 3-hydroxyvalerate into PHB led to marked molecular mobility enhancement in the biopolymers. (C) 2007 Elsevier Ltd. All rights reserved.