AbstractThe aim of this study was to evaluate the effect of different morphologies of solvent-exchanged (NFCSE), spray-dried (NFCSD), and freeze-dried (NFCFD) nano-fibrillated cellulose on the susceptibility to surface modification with the acetic anhydride/pyridine system. The degree of substitution (DS), morphology, degree of crystallinity (Icr), hydrophobicity, and thermal stability of acetylated products were examined. Acetylated NFCSD and NFCFD had higher DS than acetylated NFCSE, suggesting that drying pre-treatment increased the susceptibility of NFC for acetylation. The morphology of acetylated NFCFD and NFCSD with higher DS was different from unmodified samples, while that of NFCSE was not affected by acetylation. Microspheres of acetylated NFCSD started to dissolve when the highest DS was reached. As opposed to unmodified NFCFD, the nanofibrillar units of acetylated NFCFD became individualised at lower DS. Acetylated samples had lower Icr than the unmodified samples. A significant increase in the contact angle was observed at higher DS of acetylated NFC samples. Acetylation markedly elevated the thermal stability of the acetylated NFC samples.