The multilayer formation between polyelectrolytes of opposite charge offers possibility for creating new tailored materials. Exchanging one or both components for charged nanofibrillated cellulose (NFC) further increases the variety of achievable properties. We explored this by introducing unmodified, low charged NFC and high charged TEMPO-oxidized NFC. Systematic evaluation of the effect of both NFC charge and properties of cationic polyelectrolytes on the structure of the multilayers was performed. As the cationic component cationic NFC was compared with two different cationic polyelectrolytes, poly(dimethyldiallylammoniumchloride) and cationic starch. Quartz crystal microbalance with dissipation (QCM-D) was used to monitor the multilayer formation and AFM colloidal probe microscopy (CPM) was further applied to probe surface interactions in order to gain information about fundamental interactions and layer properties. Generally, the results verified the characteristic multilayer formation between NFC of different charge and how the properties of formed multilayers can be tuned. However, the strong nonelectrostatic affinity between cellulosic fibrils was observed. CPM measurements revealed monotonically repulsive forces, which were in good correspondence with the QCM-D observations. Significant increase in adhesive forces was detected between the swollen high charged NFC. (C) 2011 Elsevier Inc. All rights reserved.