Ceramic foams with extensive interconnected pores have great application potential in high-temperature particulate matter (PM) capture. Considering that there are still challenges to synthesize ceramic foams with efficient filtration, a novel hierarchical-structured alumina foam with three-dimensional (3D) reticular architecture has been fabricated via combining chemical grafting pore-forming agent and polyurethane (PU) foaming technology. Carbon black is grafted with carbamate functional groups in order to enable a better dispersion in highly viscous PU. Submicrometer and micrometer-sized pores on the cell walls are observed in hierarchical-structured ceramic foams. The resulting alumina foam exhibits 95.2% removal efficiency for PM particles and low pressure drop of only 50Pa when grafted carbon black content is 3wt%. This filtration performance is much higher than that of existing ceramic materials. These features, combined with our experimental design strategy, provide a new insight to design high-temperature PM filtration materials with durable high performance.