We investigate the electronic structure of over-coordinated defects in amorphous silicon via density-functional total-energy calculations, with the aim of understanding the relationship between topological and electronic properties on a microscopic scale. Maximally localized Wannier functions (MLWF)are computed in order to characterize the bonding and the electronic properties of these defects. The five-fold coordination defects give rise to delocalized states extending over several nearest neighbors (NNs), and therefore to very polarizable bonds and anomalously high Born effective charges for the defective atoms.