[en] Highlights: • A MWCNTs/rGO/ZnO quantum dots intercalation nanoballs decorated 3D hierarchical architecture is fabricated on Ni foam. • Large numbers of ZnO quantum dots are intercalated by rGO sheets to construct hierarchical nanoballs. • Improved mechanical, kinetic and electrochemical properties are found. • The strong interfacial effect makes the material can be used for selective detection of dopamine, ascorbic acid and uric acid. - Abstract: ZnO quantum dots (QDs), reduced graphene oxide (rGO) and multi-walled carbon nanotubes (MWCNTs) are always used in sensors due to their excellent electrochemical characteristics. In this work, ZnO QDs were intercalated by rGO sheets with cross-linked MWCNTs to construct intercalation nanoballs. A MWCNTs/rGO/ZnO QDs 3D hierarchical architecture was fabricated on supporting Ni foam, which exhibited excellent mechanical, kinetic and electrochemical properties. The intercalation construction can introduce strong interfacial effects to improve the surface electronic state. The selectively determinate of uric acid, dopamine, and ascorbic acid by an electrode material using distinct applied potentials was realized.