We performed β-NMR spectroscopic studies on 12B which was implanted into MgB2 to get insight into the local electronic structure of this high-temperature superconducting material. By measuring electric field gradients we probed the electronic charge distribution anisotropy around boron in this solid and thus obtained experimental information about the bonding by p electrons. Besides the absolute value, the sign of the electric field gradient was also experimentally determined. By comparison with quantum chemical calculations, some of which were performed in the present work, and with results from conventional NMR spectroscopy on 11B we were able to identify regular boron lattice sites as well as interstitial sites. © 2007 The American Physical Society.