In the present study, PHB film was prepared by thermo-compression molding and PHB nanofibers mat was produced through electrospinning process. The nanofibers morphology was confirmed by SEM. The film and nanofibers crystallinity degree was estimated by different methods. FTIR and WAXD indicated that PHB film is more crystalline than PHB nanofibers. However, DSC analysis suggested that a PHB nanofibers phase change might occur while the temperature rises. SAXS indicated that PHB film and nanofibers have low electron density contrast between the alternating crystalline and amorphous layers. The influence of nanofiber morphology on the mechanical, surface and thermal properties was also shown in TG analysis, tensile tests and contact angle measurements.