LDHs in atomic thickness (mono-/bi-layers) usually exhibit novel physicochemical properties, especially in surface-dependent energy storage and catalysis areas. However, the thickness of the commonly reported 2D LDHs is in nanoscale and the bottom-up synthesis of atomically thin LDHs is rarely reported. Herein, high-quality atomically thin layered NiFe-LDHs assembled 3D microspheres were synthesized via a rational designed reaction system, where the formation of atomically thin building blocks was controlled by the synergetic effects of released carbonate anions and butanol. Furthermore, the complexant and solvents played important effects on the process of coprecipitation and the assembling of LDHs. Due to the nature of atomically thin LDHs nanosheets and unique 3D hierarchical structures, the obtained microspheres exhibited excellent electrocatalytic oxygen evolution reaction (OER) activity in alkaline medium with an onset overpotential (0.435 V, which is lower than that of common LDHs) and good durability. The as-prepared 3D NiFe-LDHs microspheres were also firstly used as supercapacitor materials and displayed a high specific capacitance of 1061 F g(-1) at the current density of 1 A g(-1). (C) 2016 Elsevier B.V. All rights reserved.