This study presents the non‐isothermal behavior of poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV) biodegradable films with 1–5 wt% of cellulose nanoparticles (CNs) manufactured by solution casting using N,N‐dimethylformide and chloroform as the solvents. X‐ray diffraction and scanning electron microscopy with field emission gun were performed for CNs in order to determine its morphology and crystalline properties. The effect of non‐isothermal crystallization of PHBV and its nanocomposites was studied using differential scanning calorimetry technique. The incorporation of CNs increases the crystallization rate with up to 3 wt%. Structural parameters were studied using positron annihilation lifetime spectroscopy and small‐angle X‐ray scattering. The free volume does not change upon CNs addition in spite of form less perfect crystals and increase the lamellar thickness. POLYM. COMPOS., 40:3156–3165, 2019. © 2018 Society of Plastics Engineers