TiAl-based porous microfiltration membranes are expected to be the next-generation filtration materials for potential applications in high-temperature flue gas separation in corrosive environments. Unfortunately, the insufficient high-temperature oxidation resistance severely limits their industrial applications. To tackle this issue, a Ti-40Al-10Nb-10Cr porous alloy was fabricated for highly effective high-temperature flue gas purification. Benefited from microstructural changes and the formation of two new phases, the Ti-40Al-10Nb-10Cr porous alloy demonstrated favorable high-temperature anti-oxidation performance with the incorporation of Nb and Cr high-temperature alloying elements. By the separation of a simulated high-temperature flue gas, we achieved an ultra-high PM-removal efficiency (62.242% for PM and 98.563% for PM>2.5). These features, combined with our experimental design strategy, provide a new insight into designing high-temperature TiAl-based porous materials with enhanced performance and durability.