A series of five silica supports with different pore diameters were functionalized in two steps by post-grafting, producing three types of material: (1) initial supports with pores smaller than 4 nm are heterogeneously functionalized because of steric effects; (2) when the pores range from 5 to 20 nm in diameter, a homogeneous organic monolayer is grafted onto the silica skeleton; and (3) when the pores are larger than 30 nm, an organic multilayer covalently linked to the surface is obtained. These hybrid materials were then used to extract uranium from a sulphuric solution. Our results show that the efficiency, capacity and selectivity of the extraction can be controlled through the effect the initial pore size has on the organic structures that form therein. After regeneration moreover, these materials can be reused with the same efficiency.