CeO 2 –ZrO 2 –Al 2 O 3 composite oxides supported palladium catalysts (Pd/CZA) are promising candidates for catalytic oxidation reactions. However, the efficient and stable oxidation of methane over Pd-based catalysts remains a longstanding challenge. Herein, we present a facile strategy to boost the catalytic performance of Pd/CZA through elaborately tuning the phase structure of supports. Calcining supports at relatively high temperatures (1200, 1300 °C) induced the phase transition of alumina (from γ-to α-) and the development of CeO 2 –ZrO 2 solid solution (CZ). The weak interaction between α-Al 2 O 3 and PdO resulted in an improved reducibility of catalysts. Meanwhile, the higher oxygen mobility originated from well-crystallized CZ phase contributed to the reoxidation of Pd to PdO, giving rise to abundant surface active Pd2+ species. Coupled with the hydrophobicity of α-Al 2 O 3 , the catalyst prepared with CZA supports calcined at 1300 °C demonstrated an excellent low-temperature activity, astounding stability and greatly enhanced water resistance towards methane combustion. [Display omitted] • Phase structure of Ce–Zr–Al supports was tuned with calcination temperature. • α-Al 2 O 3 phase gave rise to an improved reducibility and water-resistance. • Well-crystallized Ce–Zr solid solution phase contributed to the reoxidation of Pd0. • Synergy of α-Al 2 O 3 and Ce–Zr solid solution invoked a high-performance of Pd/CZA. [ABSTRACT FROM AUTHOR]