The regular and yttrium-doped spherical β-phase nickel hydroxides were synthesized by means of chemically co-precipitation. The yttrium-doping with long needle-like nanocrystallites observed by TEM promoted the formation of the spherical nickel hydroxide with the larger diameter of about 5μm. The discharge capacity of the yttrium-doped spherical nickel hydroxide was measured to be slightly lower than that of the regular spherical nickel hydroxide at room temperature. At temperatures of above 50°C, however, the discharge capacity of the yttrium-doped nickel hydroxide is much higher than that of the regular spherical nickel hydroxide. The improvement of discharge capacity at elevated temperatures was contributed to the increase of the charge acceptance of yttrium-doped nickel hydroxide. The formation of an yttrium-rich surface layer on nickel hydroxide particles raised the oxygen evolution over-potential, leading to performance improvements of the nickel hydroxide electrode. The improvement of high temperature charge acceptance of yttrium-doped nickel hydroxide remarkably contributed to the high temperature charge–discharge efficiency of the nickel–metal hydride (Ni–MH) batteries with a commercial AAA size.