We report a comprehensive study on the interactions between cationic surfactant homologues C(n)TAB (n = 12, 14, and 16) with negatively charged cellulose nanocrystals (CNCs). By combining different techniques, such as isothermal titration calorimetry (ITC), surface tension, light scattering, electrophoretic mobility, and fluorescence anisotropy measurements, we identified two different driving forces for the formation of surface induced micellar aggregates. For the C(12)TAB surfactant, a surfactant monolayer with the alkyl chains exposed to the water is formed via electrostatic interactions at low concentration. At a higher surfactant concentration, micellar aggregates are formed at the CNC surface. For the C(14)TAB and C(16)TAB systems, micellar aggregates are formed at the CNC surface at a much lower surfactant concentration via electrostatic interactions, followed by hydrophobic interactions between the alkyl chains. At higher surfactant concentration, charge neutralization and association of the surfactant decorated CNC aggregates led to flocculation.