The impact of Fröhlich scattering on β ‐Ga 2 O 3 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 ‐Ga 2 O 3 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.