These studies are related to the development of an innovative solution for the extraction of transuranium elements from high radioactive level acid solutions. In this frame, advanced silica hybrid materials were developed by hydrolysis and condensation of molecular species functionalised with complexing functions, leading to the improvement of solideliquid extraction techniques.The influence of the nature of the complexing organic groups, of the microstructure and of the extractant loading in the condensed matter on the distribution coefficient is determined in the case of americium and plutonium extractions from nitric acid media. Preliminary studies on the americiumeeuropium separation using these materials were also tackled.