Relationships between composition- and temperature-dependent intermolecular interactions and cold crystallization behaviors of poly(3-hydroxybutyrate) (PHB)/ cellulose acetate butyrate (CAB) blends have been investigated mainly by infrared (IR) spectroscopy, together with differential scanning calorimetry, and wide-angle X-ray diffraction (WAXD). Weak intermolecular hydrogen bondings between OH groups in CAB and C=O groups in amorphous part of PHB define as inter were detected in OH stretching bands of the blends. These interactions occur in the blends with high CAB content (w(CAB)) and highly depend on temperature. For all the blends having 0.2 <= w(CAB) <= 0.7, when temperature is raised (e.g., above 90 degrees C for the blend with w(CAB) = 0.5) the cold crystallization of PHB was discerned, as evidenced by an increase of the absorbance of the band due to C=O stretching in the crystal field. The crystallization was found to involve the dissociation of inter and transformation of inter into intramolecular hydrogen bondings within PHB and within CAB as summarized in Table 2 in this text, which promotes the crystallization and enhances stabilization of the crystals. Consequently, the crystallization of the PHB is influenced by exchanges of the hydrogen bondings as described above with raising temperatures. X-ray diffraction from PHB crystals in the blends show a remarkable decrease of crystallinity with w(CAB) and eventually disappear when w(CAB) >= 0.8. (C) 2010 Elsevier Ltd. All rights reserved.