Post treatment of metal-organic frameworks (MOFs) is widely employed to develop efficient electrocatalysts with better catalytic properties. But the complex processes of post treatment generally led to the collapse of the original structures of MOFs, making the preservation of their pristine hierarchical porous structure a great challenge. Herein, we propose the strategy of alkali treatment of Ni-MOF to transform it into Ni(OH)2 with similar morphology and enhanced electrocatalytic properties for methanol oxidation reaction (MOR). The structure and electrocatalytic properties of as-obtained Ni(OH)2 nanostructured flowers were seriously depended on the alkali concentrations. As the result, Ni(OH)2 obtained from Ni-MOF treated by 0.25 M NaOH (noted as Ni(OH)2 -0.25) performs 1.5 and 2.5 times larger current density than those of Ni(OH)2 -0.025 and Ni(OH)2 -0.5 for MOR. Moreover, the electrocatalytic process and mechanism of MOR on the catalyst of Ni(OH)2 -0.25 are also revealed. Hence, this ex situ conversion strategy of alkali treatment for Ni-MOF uncovered the transformation of MOFs in alkaline solution and develops robust electrocatalyst for practical application of methanol fuel cells.