Single-crystal growth of (100) beta-Ga2O3 and the attempt to grow GaP on it by hydride vapor phase epitaxy (HVPE) is been described. The phase purity and (100) orientation of the crystal is confirmed by X-ray diffraction (XRD). The selected area electron diffraction pattern confirms the monoclinic structure with a C2/m space group of beta-Ga2O3. Raman results reveal the stretching and bending vibrations of Ga-O and Ga-O-Ga octahedrons, respectively. The wafer exhibits approximate to 80% optical transmission and surface roughness of approximate to 5 nm. GaP layers are grown on (100)-oriented beta-Ga2O3 substrates by HVPE. The GaP/beta-Ga2O3 heterostructures are characterized using XRD and Raman spectroscopy. Diffraction peak at (111) confirms the zinc blende phase of GaP. The longitudinal optical (405 cm-1) and transverse optical (368 cm-1) phonon modes in the Raman spectra confirm the crystalline GaP. Further optimization is expected to enhance the crystalline quality of the GaP layer on the Ga2O3 wafer. The potential of GaP/(100) beta-Ga2O3 heterostructures are highlighted.