The study presents an investigation on the conformational changes and the interaction between the components of a new network structure based on a polymer system with spiroacetal moieties, namely poly(itaconic anhydride-co-3,9-divinyl-2,4,8,10-tetraozaspiro [5.5] undecane) (PItAU), and riboflavin (Rb) as low molecular mass gelator, in order to tailor its properties according to a targeted application. Therefore, the physicochemical characteristics of the new PILAU_Rb compound were evaluated in terms of thermal stability, microscopic, spectroscopic and dielectric properties. The maintaining of the thermal stability of the new compounds close to that of the starting copolymer was confirmed. The fluorescence emission and circular dichroism spectroscopy attested that the chemical reaction between PItAU and Rb did not destroyed the structure and the properties of Rb. Additionally, the dielectric spectroscopy investigation evidenced that the presence of Rb could lead to controlling the network architecture and the chain connectivity, which is critical for further self-aggregation organisation and network formation.