The electronic structure and tuning of work function (WF) by electronic excitations (EEs) induced by swift heavy ions (SHIs) in anatase niobium-doped titanium dioxide (NTO) thin films is reported. The densities of EEs were varied using 80 MeV O, 130 MeV Ni and 120 MeV Ag ions for irradiation. The EE-induced modifications in electronic structure were studied by O K-edge and Ti L3,2 edge absorption spectra using near edge X-ray absorption fine structure (NEXAFS) spectroscopy. The reduction of hybridized O 2p and Ti 3d unoccupied states in the conduction band with a decrease in energy of the crystal field strength of ∼ 480 meV and the correlated effect on the decrease in the WF value of ∼ 520 meV upon increasing the total energy deposition in the lattice are evident from the study of NEXAFS and scanning Kelvin probe microscopy (SKPM), respectively. The observed stiffening in the low frequency Raman mode (LFRM) of ∼ 9 cm(-1) further validates the electronic structure modification under the influence of EE-induced strain in TiO6 octahedra. The reduction of hybridized valence states, stiffening behavior of LFRM and decrease in WF by nano-crystallization followed by amorphization and defects in NTO lattice are explained in terms of continuous, discontinuous amorphous ion tracks containing intestinally created defects and non-stoichiometry in the lattice. These studies are very appropriate for better insights of electronic structure modification during phase transformation and controlled Fermi level shifting, which plays a crucial role in controlling the charge carrier injection efficiency in opto-electronic applications and also provides a deeper understanding of the involved physical processes.