NiII and MnIII Schiff base complexes (Salophen-Ni and Salophen-MnCl) bearing a pending carboxylic group were prepared and characterized. Both complexes were grafted onto a mesoporous amino-functionalized SBA-15 silica, by formation of an amide function between the propylamine groups of the support and the carboxylic acid functions of the salophen ligand (corresponding respective to 1.30 wt.% of Ni and 1.06 wt.% of Mn). The co-catalytic behaviour of the free and grafted complexes was then evaluated in the CO2 cycloaddition reaction onto styrene oxide, using tetra-butylammonium bromide (n−Bu4NBr) as the main catalyst. In homogeneous conditions, the MnIII Schiff base complex and the NiII one, to a lesser extent, behave as efficient co-catalysts for this reaction (styrene conversion of 100 % and 65 % respectively after 3 h at 120 °C, under 15 bars of CO2). Upon immobilization at the surface of the amino-functionalized SBA-15, we showed that the co-catalytic activity of the less efficient one, i. e. Ni2+ salophen complex, could be enhanced (reaching a full conversion after 7 h), hence highlighting a potential synergistic effect between the unused amine functions of the support and the Ni2+ salophen co-catalyst. Both salophen complexes were successfully re-used in homogeneous conditions or after their immobilization without any appreciable loss of activity. This work is only a first step towards a completely heterogeneous catalytic system, in which the tetraalkylammonium halide catalyst and the metal-salophen co-catalyst will both be covalently anchored on the same support