Comprehensive SummaryDeveloping new catalysts for highly selectivity and conversion of saturated C(sp3)–H bonds is of great significance. In order to obtain catalysts with high catalytic performance, six Eu‐based MOFs with different structural characteristics were obtained by using europium ions and different organic acid ligands, namelyEu‐1~Eu‐6.Eu‐1,Eu‐2andEu‐3featured three‐dimensional structures, whileEu‐4andEu‐5featured two‐dimensional structures. Differently, a one‐dimensional chain structure ofEu‐6was obtained by changing the ligand. All the six MOFs were applied to the catalytic reaction of C(sp3)–H bond, and it was found that the catalytic effect was gradually enhanced with the decrease of dimension and the increase of the size of channels. As expected,Eu‐6showed the highest selectivity (~99%) and conversion (~99%). Moreover, catalytic cycling and stability tests showedEu‐6can be a reliable catalyst.