In this work, we reported a novel synthesis of acid or base functionalized microporous organic nanotube networks (MONNs) by hyper-crosslinking core–shell bottlebrush copolymers. With a high specific surface area, excellent hierarchical porosity and site-isolation features, the resultant SO₃H– and NH₂–MONNs catalyst systems present an excellent catalytic performance for deacetalization-Knoevenagel cascade reactions.