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Herein, alkali\u2010modified hierarchical porous Na\u2010CoO<jats:sub>x<\/jats:sub>\/CN material was prepared using a novel freeze\u2010drying\u2010pyrolysis method by employing super absorbent resin\/MOF composites as templates, which generate mesopores distributed in a narrow region of 6\u223c20\u2005nm and abundant hydroxyl groups on the surface by alkali\u2010modification. At room temperature, the Na\u2010CoO<jats:sub>x<\/jats:sub>\/CN material exhibited full conversion of low concentration (1.0\u2005mg\/m<jats:sup>3<\/jats:sup>) and high throughput (240,000\u2005mL\/(g<jats:sub>cat<\/jats:sub>\u2009h)) formaldehyde while also demonstrating outstanding catalytic stability under a even higher space velocity (480,000\u2005mL\/(g<jats:sub>cat<\/jats:sub>\u2009h)). 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