This paper presents a novel strategy to address the environmental challenges associated with piezo-catalysis by developing retrievable hierarchically porous ferroelectric ceramics. The focus is on Ba0.75Sr0.25TiO3 (BST) ceramics, which are prepared using freeze casting and direct ink writing techniques. The study highlights the positive impact of introducing micro- and macro-pores on the piezo-catalytic properties of BST ceramics. Specifically, a BST ceramic with hierarchical pore channels, fabricated by combining direct ink writing and freeze casting, exhibits the highest first-order kinetic rate constant per mass of catalysts (k) of up to 2.91 min−1 kg−1 compared to bulk BST ceramics. This material also demonstrates an average H2 production rate of 848.88 nmol g−1 h−1, making it a promising candidate for water splitting and wastewater treatment applications. The hierarchical pore structure enhances the accessibility of water and reactants, leading to improved catalytic performance. The study provides a comprehensive understanding of the benefits of porous ferroelectric ceramics in piezo-catalysis, offering a green alternative to traditional powder-based catalysts.This paper presents a novel strategy to address the environmental challenges associated with piezo-catalysis by developing retrievable hierarchically porous ferroelectric ceramics. The focus is on Ba0.75Sr0.25TiO3 (BST) ceramics, which are prepared using freeze casting and direct ink writing techniques. The study highlights the positive impact of introducing micro- and macro-pores on the piezo-catalytic properties of BST ceramics. Specifically, a BST ceramic with hierarchical pore channels, fabricated by combining direct ink writing and freeze casting, exhibits the highest first-order kinetic rate constant per mass of catalysts (k) of up to 2.91 min−1 kg−1 compared to bulk BST ceramics. This material also demonstrates an average H2 production rate of 848.88 nmol g−1 h−1, making it a promising candidate for water splitting and wastewater treatment applications. The hierarchical pore structure enhances the accessibility of water and reactants, leading to improved catalytic performance. The study provides a comprehensive understanding of the benefits of porous ferroelectric ceramics in piezo-catalysis, offering a green alternative to traditional powder-based catalysts.