In this work, hydrogels composites based on reduced graphene oxide-xanthan gum and a synthetic and biodegradable polymer, poly(N-vynil-2-pyrrolidone) (XGrGoPVP) were synthesized by electron beam radiation crosslinking, in the presence of N,N’-methylenebisacrylamide (NMBA) used as a crosslinking agent. In order to investigate the influence of reduced graphene oxide on the hydrogel properties, two types of polymeric hydrogels were prepared, with reduced graphene oxide (rGo) and without reduced graphene oxide. Thermal analysis (TG/DSC) was employed to investigate the thermal behavior of these hydrogels composites. The TG curves of XGrGoPVP hydrogels showed one mass loss event, characterized by an increase of weight loss percentage up to 10 kGy. The degradation temperature was likely influenced by the addition of rGo and above 20 kGy, this parameter has decreased. The DSC data presents one endothermic peak, whose melting enthalpy obviously increased up to 10 kGy. The different absorbed dose, as well as the addition of rGo was found to influence the crosslinking process and the hydrogels thermal behavior. The polymeric hydrogel composites were investigated by FT-IR, FT-Raman spectroscopy and scanning electron microscopy (SEM). The sol-gel analysis and the swelling behaviour, as function of absorbed dose, were investigated to calculate the crosslink density and the average molecular weight between crosslinks (Mc). FT-IR and FT-Raman analysis has shown the formation of a miscible blend between the hydrogels components. The crosslinking process has been highlighted by increasing the intensity of specific absorption bands or their shifting toward lower wavenumbers, as well as throughout the formation of new C−C chemical bonds. The sol-gel analysis revealed that the minimum absorbed dose to reach the gel point is 4.9 kGy for hydrogels composites with rGo and the degradation degree was higher for the hydrogels without rGo. The swelling degree has increased with absorbed dose and reached a maximum value of 3000%. The same increase was observed when the average molecular weight between crosslinks (Mc) was determined.