Reactive flexible polyurethane (PU) foams were synthesized with two contents of hard segments (HS) and filled with multi-walled carbon nanotubes (MWCNTs), functionalized MWCNTs (f-MWCNTs) and functionalized graphene sheets (FGS). The effect of the HS content and the carbon nanofillers on the kinetics of polymerization and the kinetics of phase-separation have been studied by Fourier transform infrared spectroscopy (FT-IR) and synchrotron small-angle X-ray scattering (SAXS). A slow down on the rate of polymerization and on the development of the polymer structure due to the increase of the HS content and the inclusion of the nanoparticles was observed. Therefore, this work demonstrates that there is a relationship between the kinetics of polymerization and the kinetics of phase separation in flexible PU nanocomposite foams. SAXS data was used to generate 3D microstructures of PU nanocomposite foams and the phase-separated morphology was observed by atomic force microscopy (AFM). (C) 2012 Elsevier Ltd. All rights reserved.