Exploitation of highly efficient catalysts for photocatalytic degradation of volatile organic compounds (VOCs) under visible light irradiation is highly desirable yet challenging. Herein, well-aligned 2D Ni-MOF nanosheet arrays vertically grown on porous nickel foam (Ni-MOF/NF) without lateral stacking were successfully prepared via a facile in situ solvothermal strategy. In this process, Ni foam could serve as both a skeleton to vertically support the Ni-MOF nanosheets and a self-sacrificial template to afford Ni ions for MOF growth. The Ni-MOF/NF nanosheet arrays with highly exposed active sites and light harvesting centres as well as fast mass and e− transport channels exhibited excellent photocatalytic oxidation activity and mineralization efficiency to typical VOCs emitted from the paint spray industry, which was almost impossible for their three-dimensional (3D) bulk Ni-MOF counterparts. A mineralization efficiency of 86.6% could be achieved at 98.1% of ethyl acetate removal. The related degradation mechanism and possible reaction pathways were also attempted based on the electron paramagnetic resonance (EPR) and online Time-of-Flight Mass Spectrometer (PTR-ToF-MS) results.