In this study, cellulose nanofibrils (CNF) of high charge (H-P-CNF) and screened size (H-P-CNF-S) were fabricated by increasing the charge of phosphorylated cellulose nanofibrils (P-CNFs) during the pre-treatment step of CNF production. Results show that the H-P-CNF have a significantly higher charge (3.41 mmol g−1) compared with P-CNF (1.86 mmol g−1). Centrifugation of H-P-CNF gave a supernatant with higher charge (5.4 mmol g−1) and a reduced size (H-P-CNF-S). These tailored nanocelluloses were added to polyvinyl alcohol (PVA) solutions and the suspensions were successfully coated on porous polysulfone (PSf) supports to produce thin-film nanocomposite membranes. The humid mixed gas permeation tests show that CO2 permeability increases for membranes with the addition of H-P-CNF-S by 52% and 160%, compared with the P-CNF/PVA membrane and neat PVA membrane, respectively.