One-dimensional, two-dimensional and three-dimensional Ni-containing metal-organic coordination polymer (1D-Ni, 2D-Ni and 3D-Ni MOCP) catalysts were solvothermally synthesized and used for isomerization of isobutene. These catalysts showed the same conversion of isobutene and selectivity for 2-butene as homogeneous catalysts. At the same time, 1D-Ni catalyst evacuated at 100 °C revealed the conversion of isobutene and selectivity to 2-butene were up to 89.2% and 100.0%, respectively. Moreover, the results demonstrated that the conversion of isobutene was different depending on metal coordination mode, dimension of coordination polymer, and the reaction pressure. In addition, The MOCP catalysts were relatively environmentally friendly, and easily recovered and recycled. Finally, the mechanism of metal hydride addition elimination was proposed.