In this work, we investigated the structural evolution, electronic and magnetic properties of Cr2Gen− clusters for n = 15–20 by using density functional theory (DFT) calculations. Low‐energy structures for these clusters were fully searched through a self‐developed genetic algorithm code combined with DFT calculations. The calculations show that all the two Cr atoms prefer to stay together to form a strong CrCr bond, which—except for size 20—is shorter than the nearest neighbor distance in Cr bulk. Sizes 15 and 16 adopt a wheel‐like structure as the structural motif with the extra Ge atoms capped on the top, while larger sizes (n = 17–20) prefer fullerene‐like Cr2@Ge12 motifs. From the results of the average binding energies of Cr2Gen−, one can conclude that it is easier to form larger size clusters. In these lowest‐lying isomers except for size 16, the two Cr atoms contribute opposite magnetic moments for the total magnetic moments of 1 μB, showing an antiferromagnetic state.