Silica based porous liquids (PLs) are innovative and versatile liquid materials with high potential, although their application is often restricted to gas sorption. In this work, we propose to evaluate their potential interest to extract metals. For this goal, we have adapted their synthesis to provide porous liquids functionalized with thiols that are expected to chelate metallic contaminants such as lead. As the accessibility of liquids and metals to the PL’s porous network is one of the key points for their application, we developed an original Small-Angle Neutron Scattering (SANS) experiment, to verify that the porous liquid is permeable to polar liquids. Then, preliminary extraction tests have successfully been carried out, with an extraction of lead cations by complexation on one third of accessible thiols groups. This work demonstrates that the extraction of metal species by a porous liquid is possible and opens on many perspectives for optimization.