The physical state of poly(hydroxybutyrate) (PHB) in whole cells and in the form of artificial biomimetic granules has been probed using 13C nuclear magnetic resonance (NMR) spectroscopy. Studies on varying concentrations of whole cells of Alcaligenes eutrophus show that changes in the line widths of PHB in whole cells do not correlate with changes in transverse relaxation times. Solid-state magic-angle spinning NMR studies demonstrate that the line broadening results from a reduction in the static field homogeneity rather than from intrinsic properties of the PHB within the cells. Transverse and longitudinal relaxation times of PHB in whole cells and in artificial granules are similar, indicating similarities in structure and mobility.