A hollow Co 3 O 4 turtle shell-like structure (HSÀ Co 3 O 4 ) was synthesized from ZIF-67 and further employed for the first time to electrochemically real-time monitor dopamine (DA) released from living cells. X-ray powder diffraction, electron microscopy, X-ray photoelectron spectroscopy, electrochemical methods were used to study its physical and chemical properties and electrocatalytic behaviours. The as-prepared DA HSÀ Co 3 O 4 sensor accomplishes an outstanding limit of detection (LOD) of 3 nM, a broad linear range of 0.01-360 μM, good stability and high selectivity. It was further used to successfully real-time monitor DA released from living cells, demonstrating its great potential in practical applications in clinic diagnosis and bioscience research. The great sensing enhancement mechanism is investigated, revealing that the unique nanostructure not only provides a high density of active centers, but also more interestingly renders a unique mechanism by creating an atomic match between the adjacent Co ions catalysis centers and the two reaction atomic sites of DA for a fast 2-electron transfer path.