The electronic structures of lanthunum (La) incorporated hafnium (Hf)-based oxides (HfLaO) and their silicate (HfLaSiO) films were investigated by the Near Edge X-ray Absorption Fine Structure (NEXAFS) technique. The oxygen (O) K-edge spectra, which reflected the hybridized Hf 5d state with the O 2p orbital, were found to reveal features of the unoccupied state of the metal oxides, as well as the conduction-band edge. We also found that, while La incorporation into the Hf-based oxides simply changed the features of the conduction-band structure, subsequent thermal annealing of the La-incorporated films led to a conduction-band edge shift due to an interface silicate reaction and/or local bond rearrangement depending on the La concentration and annealing temperature. The impact of La incorporation into the Hf-based high-k materials on the electronic structure is discussed by taking into account the intrinsic nature of these metal oxides.