The electronic structure of nearly stoichiometric Ni–Mn–Sn and Ni–Mn–In surface is investigated by inverse photoemission and photoemission spectroscopy. Comparison of the experimental and calculated inverse photoemission spectra shows that the dominant feature is related to Mn 3d-like states. The overall shape and peak position of the theoretically obtained spectra show good agreement with the experimental ultraviolet photoemission valence band spectra. The changes in the composition dependent ultraviolet photoemission spectra reveal the change in degree of Ni 3d and Mn 3d band hybridization. Both inverse photoemission and ultraviolet photoemission study show a rigid band shift between Ni2MnIn and Ni2MnSn because of band filling, due to increase in the number of 5p electrons from In to Sn. Mn 2p and 3s core-level reveal unambiguous existence of exchange splitting in both the materials.