The impact of Fröhlich scattering on β‐Ga2O3 Schottky barrier diodes (SBDs) electron mobility, particularly at high temperatures, is investigated. This scattering is crucial due to electron–polar optical phonon interactions. Temperature‐dependent I–V characteristics of a β‐Ga2O3 SBD from 300 to 473 K showed significant current reduction due to electron–polar optical phonon scattering, supported by correlation with mobility profiles. Additionally, in situ temperature‐dependent XPS analysis revealed a notable positive shift in core‐level binding energy, attributed to heightened electron–phonon interactions. This study provides crucial insights into carrier transport mechanisms, essential for power device design and operation.