Niobium and cerium dopants of mesoporous cellular foams, MCF, have been recently considered as promoters enhancing the basicity of amino-organosilanes anchored to the supports. Thus, the knowledge of acid-basic properties of niobium and cerium containing MCFs is important. Therefore, in this work monometallic (Ce and Nb) and bimetallic (Ce + Nb) materials based on MCF were investigated by means of NO and pyridine adsorption combined with infrared (FTIR) and electron spin resonance (ESR) spectroscopies as well as test reactions. The properties of bimetallic materials strongly depended on the method of impregnation (one-pot vs. step-by-step procedure). If niobium was included in step-by-step method (first niobium and next cerium sources - Ce/Nb/MCF) the Nb species were incorporated to silica skeleton and ceria surrounded some of the framework niobium species (NbO-) enhancing the acidic strength of tetra-coordinated niobium cations playing the role of Lewis acid sites (LAS). One-pot modification (simultaneous impregnation with Nb and Ce sources - CeNb/MCF) resulted in the formation of niobium and cerium oxides showing synergistic interaction. In this system ceria was more defected than in Ce/Nb/MCF sample and acidic strength of niobium species (LAS) was lower.