Hybrids based on the copper-based metal-organic framework (MOF) HKUST-1 and graphene-like (GL) materials have been synthesized at different concentrations of GL, and investigated by means of solid state nuclear magnetic resonance (ssNMR) and X-rays absorption techniques (NEXAFS and XANES) with the aim of elucidating the effect of the hybridization on the structural properties of HKUST-1. The comparative analysis of ssNMR and X-ray absorption spectra recorded on parent materials (GL materials and pure HKUST-1) and on the hybrids indicates that the overall structural features of HKUST-1 are preserved in the presence of increasing GL amounts (up to 30 wt.%) and confirms that the framework development is not massively altered by the presence of GRMs in the synthetic medium.