Higher alcohol synthesis (HAS) from CO2, instead of syngas (CO/H2), is a highly desirable reaction with the potential of alleviatingAbstract: anthropogenic CO2 emissions. However, highly active and selective catalysts for the conversion of CO2 to HAS remain elusive and poorly understood, their development presenting a formidable task. Rh-based catalysts have shown one of the best selectivities for ethanol, especially when doped with first-row transition metals (Fe or Mn) as well as alkali metals (Li and Na). By a Surface Organometallic Chemistry approach we have synthesized a family of size homogeneous silica-supported Rh nanoparticles doped with promoters (RhM@SiO2, M = Fe, Li, Na). We aim at conducting ex-situ and in-situ X-ray absorption spectroscopy (XAS) to identify the speciation and the activ sites of such catalysts. In the future we hope to use the outcomes of these experiments to rationally design highly selective catalysts for the synthesis of higher alcohols from CO2.