Complex oxides are an intriguing field of solid-state research, as they can exhibit a wide variety of functional properties, such as ferroelasticity, ferroelectricity, ferro- and antiferromagnetism or an even more complicated type of magnetic ordering, the combination or interaction of those ferroic properties (multiferroicity), high spin polarization, or high-temperature superconductivity. Thus they are prospective candidates for future materials in microelectronics. It is a matter of fact that the performance of such oxide-based devices depends mainly on transport properties, which in turn depend on the distribution and density of intrinsic or extrinsic electronic interface states across the device structure. The present thesis focuses on the identification and characterization of such electronic properties by two different photoassisted spectroscopy techniques: surface photovoltage spectroscopy and photoelectron spectroscopy. This work especially deals with perovskite oxides, namely with the model perovskite strontium titanate (SrTiO3) as a substrate and three differently doped lanthanum manganite thin films (10-15 nm thickness) grown by pulsed laser deposition (PLD) on the SrTiO3 substrate(La0.7Sr0.3MnO3, La0.7Ca0.3MnO3, La0.7Ce0.3MnO3). The first part aims at the identification of electronic surface and interface states at the free SrTiO3 surface as well as at the three different lanthanum manganite/SrTiO3 interfaces. For that purpose three different experimental realizations of the surface photovoltage spectroscopy technique were implemented and employed: photoelectron spectroscopy under additional optical excitation, the capacitive detection of the photoinduced displacement current in a parallel-plate capacitor geometry under modulated optical excitation, and the classical Kelvin probe technique. The methods are evaluated comparatively with respect to their suitability to analyze the given oxidic interfaces. The main result of this first part is a map of the energetic positions and relaxation time constants of the surface states at the SrTiO3 surface as well as of the interface states at the lanthanum manganite/SrTiO3 interfaces within the SrTiO3 bandgap. The interface states were classified into film- and substrate-induced states and it could be demonstrated that an appropriate annealing procedure can dramatically decrease their densities. The second part tackles the problem of the manganese valence and the doping type of di- and tetravalent-ion-doped LaMnO3. The question whether the insulating parent compound LaMnO3 becomes an electron-doped semiconductor after doping with tetravalent cations such as Ce4+ - which would be in analogy to the well-established hole doping after partial substitution of La3+ by divalent cations such as Sr2+ or Ca2+ - has been discussed controversially in the literature so far. Due to the physics of the manganite crystal lattice the question can also be formulated in a different way: Can part of the manganese ions be driven from the Mn3+ state towards the Mn2+ state without any crystal instabilities or phase separation phenomena? In order to contribute to the clarification of this question, an extensive X-ray- and UV-photoelectron spectroscopy (XPS/UPS) investigation was performed. The three differently doped lanthanum manganite thin films were comparatively studied considering the exchange splitting of the Mn 3s core level line, which is a linear function of the Mn valence, as measured by XPS and the work function as extracted from UPS. All measurements were performed at different states of deoxygenation after heating in ultrahigh vacuum and reoxidation after heating in a pure oxygen atmosphere. Strong evidence for electron doping of the La0.7Ce0.3MnO3 film after deoxygenation was found. Furthermore, the reversible tunability of the Mn valence by variation of the oxygen content could be demonstrated for both tetravalent- and divalent-ion-doped lanthanum manganite films.