The accessibility of metal(II) complexes in 2D hexagonal mesostructured porous silicas obtained by direct synthesis is controlled using an appropriate organosilane ligand. This is exemplified here using copper(II) as a transition metal probe and a neutral or negatively charged ligand: N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, L-A, and, N-salicylaldimine-propylamine-trimethoxysilane, L-B(-), respectively. L-A leads to inaccessible complexes located into the pore wall and called "embedded" sites here where silanolate groups from the siliceous network block the access to Cu(II) ions. By contrast, L-B(-) generates accessible complexes, named "showing-on" sites here. The copper-containing silicas were synthesized with various metal molar ratios (M/SiO2 = 0.5-3%) in basic media, with cetyltrimethylammonium p-toluenesulfonate (CTATos) as template and with sodium silicate solution as silicon source. A soft template extraction procedure has been developed to preserve the complex integrity of the showing-on copper sites during the treatment. The embedded copper(II) and nickel(II) sites were compared. Materials containing embedded, showing-on, and grafted sites were also compared with regard to pore size, surface polarity, and metal leaching. The material containing showing-on sites was found to be catalytically active for the hydroxylation of phenol into catechol and hydroquinone. Both textural and structural properties of the material and the copper sites were investigated using XRD, TEM, N-2 sorption isotherms, TGA, FT-IR, UV visible, and EPR spectroscopies.