It deals with preparation, characterization, and catalytic testing of Rh supported catalysts based on MOFs using hydroformylation as a model reaction. The influence of the MOF support on the catalytic performance (Structure-Catalytic Property-Relationships) is emphasized. Different MOF structures and pore sizes were synthesized, Rh immobilized, characterized, and tested. Results show that single site catalysts are achieved. The catalytic performance is affected by the structure, texture, and porosity of the MOF support. The linker orientation is of importance leading to single-file diffusion.