In this article, we report the morphology and thermal, mechanical and physical properties of poly(3‐hydroxybutyrate) (PHB)/curaua composites containing triethyl citrate (TEC) as the plasticizer. The composites were prepared by mechanical mixing using pristine and chemically treated fibers (10 wt %) and TEC (30 wt %) and characterized by differential scanning calorimetry, dynamic mechanical analysis, X‐ray diffraction, small angle X‐ray scattering, polarized optical microscopy, scanning electron microscopy, tensile tests, impact resistance test, thermodilatometry, and thermal conductivity measurements. The curaua fibers acted as nucleating agent and strongly influenced the morphology of the crystalline phase of PHB, increasing the lamella thickness, decreasing the crystal size and inducing spherulite–axialite transition. These characteristics of the PHB crystalline phase determined all the properties of the composites. The tensile properties of the composites were comparable with those of neat PHB, while the impact resistance of composites was comparable with that of plasticized PHB. The higher heat capacity and thermal expansion coefficient and the lower thermal conductivity of the composites compared with neat PHB reflect the morphological changes in the PHB crystalline phase. The strategy of developing a green polymeric material from ecofriendly components exhibiting a good balance of properties by combining curaua fibers, TEC, and PHB was successful. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44676.