B-Ga2O3 is one of the emerging semiconductor materials with high breakdown field strength (~ 8 MV/cm) and ultrawide-bandgap (UWBG) 4.9 eV. Therefore, B-Ga2O3 and related compound semiconductors are ideal for power electronics and deep/vacuum ultraviolet-wavelength photodetector applications. High-crystal-quality B-Ga2O3 semiconductor materials epitaxially deposited on the various substrate are prerequisites for realizing any practical application. However, it is still challenging to grow high-crystal-quality V-Ga2O3 layer and to integrate B-Ga2O3 with other semiconductor materials by direct epitaxy. Understanding the epitaxial relationship of the integrated oxide heterostructure and the substrate used helps to shed light on the feasibility of heterojunctions formation for photonic applications, such as the ultraviolet-wavelength photodetectors developed in this thesis. By optimizing pulsed laser deposition (PLD) conditions, such as laser energy, ambient gas, pressure, etc., a single-crystalline oxide heterostructure were successfully integrated into a photonic platform. This included p-NiO/n-B-Ga2O3/a-Al2O3, B-Ga2O3/y-In2O3/a-Al2O3, and B-Ga2O3/TiN/MgO structures. The epitaxial thin film crystallographic and chemical properties were investigated by different characterization techniques. The high-resolution X-ray diffraction (HRXRD) was applied to study the heterostructures’ epitaxial orientation relationship by out-of-plane XRD w-2θ-scan and asymmetric skew ɸ-scan. The lattice-mismatch at the heterostructure interfaces were examined and the crystal quality of the epitaxial thin films were measured by means of full-width at half-maximum (FWHM) fitting. Scanning-TEM energy-dispersive X-ray spectroscopy (STEM-EDX) was applied to qualitatively study the chemical elements’ spatial distribution. Rutherford backscattering spectroscopy (RBS) was applied to study the epitaxial thin film chemical composition, material stoichiometry, and inter-diffusion. The X-ray photoelectron spectroscopy (XPS) was applied to study the conduction and valence band offsets which is essential to determine the types of heterostructures formed. Finally, the p-NiO/n-B-Ga2O3/a-Al2O3 B-Ga2O3/y-In2O3/a-Al2O3, and B-Ga2O3/TiN/MgO epitaxial thin-film were fabricated into ultraviolet-wavelength photodetectors. The wavelength-dependent and power-dependent characterizations were applied to measure the cut-off wavelength and the peak responsivity. The time response characterization was applied to measure the photodetectors’ responses to pulse signals, and the rise and decay times were fitted by a double exponential function.