Semiconductors with ultrawide bandgap (E g ), such as Ga 2 O 3 , can be applied, for example, in power electronics and optoelectronic devices due to their high breakdown voltage and transparency, respectively. [1][2][3] Aside this, semiconductors with ultrawide bandgap are also of increasing interest for solar energy conversion. For example, Ga 2 O 3 layers can serve as passivation, transparent ohmic contact or charge-selective contact layers as shown in solar cells based on Cu(In,Ga)Se 2 , [4] c-Si, [5] or Cu 2 O [6] absorbers, respectively. Furthermore, Ga 2 O 3 is of great interest for photocatalytic water splitting. As very few examples, the role of copper and chromia-based cocatalysts on Ga 2 O 3 , [7] of mixed-phase junctions based on β-Ga 2 O 3 /α-Ga 2 O 3 , [8,9] of zinc and lead dopants in Ga 2 O 3 [10] or of nickel oxide cocatalysts on α-Ga 2 O 3 [11] for photocatalytic activity and photocatalytic water splitting were investigated empirically and by firstprinciple studies, respectively.Electronic states in the bandgap are crucial for the operation of electronic, optoelectronic, solar cell, and photocatalytic devices. Therefore, the characterization of electronic states and the study of their interactions is decisive for the engineering of electronic states and the further development of devices. Energy levels of deep defect states in Ga 2 O 3 were obtained using deeplevel transient spectroscopy (DLTS) [12,13] and Hall effect measurements at high temperatures. [14] Several transition energies were measured by cathodoluminescence spectroscopy. [15] However, reliable data about defect states and electronic transitions in Ga 2 O 3 are sparse and the characterization of electronic transitions and their impact on electronic properties of semiconductors with ultrawide bandgap over the entire E g is often challenging.Surface photovoltage (SPV) techniques provide universal tools for the highly sensitive analysis and investigation of electronic states in semiconductors. [16,17] Recently, for example, transitions and charge transfer processes were studied in c-Si/TiO 2 and CuBi 2 O 4 heterojunctions by transient [18] and modulated [19] SPV spectroscopy, respectively, and the bulk photovoltaic effect has been shown for excitation from defect states in carbon-doped GaN. [20] Incidentally, one SPV spectrum has been shown for Ga 2 O 3 in the work of Gao et al., [15] but in our opinion, the signal-to-noise ratio was insufficient to extract energy levels in a reliable manner.Fast and robust SPV measurements are carried out in the fixed capacitor arrangement [21] for achieving short resolution times (below 1 ns, [22] transient measurements) or high sensitivity (range of 100 nV, [23] modulated measurements). In the fixed capacitor arrangement, an electrode based on a transparent conducting oxide (TCO) and an insulating foil between the sample and the electrode are used for forming the measurement capacitor for capacitive out-coupling of SPV signals. However, optical absorption in the TCO electrode and in the insulating fo...