CrSin- (n = 14-18) cluster anions have been investigated by a combination of photoelectron spectroscopy (PES) and first-principles calculations. The lowest-lying structures of the clusters have been determined by a global minimum search based on the genetic algorithm, combined with density functional theory (DFT) calculations. The simulated PES spectra of the lowest-energy isomers are in agreement with the experimental results, which gives strong evidence that the correct structures have been found. While sizes n = 14 and n = 15 prefer cage-like structures based on multi-center bonding within the cage, the larger sizes adopt structures based on fullerene-type cages around the Cr atom, with the additional atoms attached to the cage surface. A Hirshfeld analysis shows that the Cr atoms act as electron donors in all clusters, thus enhancing the electron count in the cage. It also reveals that the magnetic moment of 1μB shown by all clusters is mainly contributed by the Cr atom. One interesting exception is size 17, where the Cr atom contributes a small moment antiparallel to that of the silicon cage.