High pressure structural phase transition of monoclinic paraotwayite typeα-Ni(OH)2 nanowires with a diameter of 15 nm–20 nm and a length of several micrometers were studied by synchrotron x-ray diffraction (XRD) and Raman spectra. It is found that theα-Ni(OH)2 nanowires experience an isostructural phase transition associated with the amorphization of the H-sublattice of hydroxide in the interlayer spaces of the two-dimensional crystal structure at 6.3 GPa–9.3 GPa. We suggest that the isostructural phase transition can be attributed to the amorphization of the H-sublattice. The bulk moduli for the low pressure phase and the high pressure phase are 41.2 (4.2) GPa and 94.4 (5.6) GPa, respectively. Both the pressure-induced isostructural phase transition and the amorphization of the H-sublattice in theα-Ni(OH)2 nanowires are reversible upon decompression. Our results show that the foreign anions intercalated between theα-Ni(OH)2 layers play important roles in their structural phase transition.