Nanoassemblies (NAs) with sizes ranging from 60 to 160 nm were spontaneously formed in water after mixing a host polymer (polymerized cyclodextrin (p beta-CD)) and a guest polymer (dextran grafted with lauroyl side chains (MD)). The combination of microscopy, dynamic light scattering (DLS), nuclear magnetic resonance (H-1 NMR), isothermal titration calorimetry (ITC) and molecular modelling was used to investigate the parameters which govern the association between MD and p beta-CD. Remarkably, when p beta-CD was progressively added to a solution of MD, NAs with a well-defined diameter were spontaneously formed and their diameter was constant whatever the composition of the system. According to NMR data, almost all the alkyl chains of MD were included into CDs' cavities of the polymer when the molar ratio lauroyl chain (C-12)/CD was >= 1. The hydrophobic interaction between C-12 and the hydrophobic cavities of CDs appears as the main driving force for NAs' formation, with a minor contribution arising from van der Waals' interactions. The inclusion of C-12 into beta-CD cavities is almost a completely enthalpy-driven process, whereas the MD-C-12/p beta-CD interaction was found to be an entropy-driven process. Major conclusions which can be drawn from these studies are that the interactions between the two polymers are restricted neither by the MD substitution yield, nor by the micellization of MD. The simultaneous effects of several CD linked together in p beta-CD and of many alkyl chains grafted on dextran were necessary to generate these stable NAs. (C) 2010 Elsevier Inc. All rights reserved.