Spherical Al-substituted ɑ-Ni(OH)2 with high tapping density are prepared with controlled crystallization method, where the synthesis parameters are previously calculated out according to theoretical analysis. The formation mechanism of Ni(OH)2 particles is analyzed based on theoretical calculation, the optimal conditions for the formation of spherical Al-substituted ɑ-Ni(OH)2 with high tapping density are figured out and a formula indicates the restrictions among main synthesis parameters is derived, which is reference meaningful for the synthesis of commercialized electrode powders. Synthesized by using the calculated parameters, the obtained ɑ-Ni(OH)2 shows uniform spherical morphology, high crystal phase purity and reasonable high tapping density of 1.37 g cm−3, which demonstrates the feasibility of the derived formula. Since the electrical conductivity of the pure Ni(OH)2 is quite low, 5 wt% of CoOOH are coated on the ɑ-Ni(OH)2 surface to improve their electrochemical performances. The synthesized CoOOH coated ɑ-Ni(OH)2 shows relative high specific capacity of 327 mAh g−1 at 0.1 C and acceptable high-rate dischargeability. The simultaneously achieving of high tapping density and high specific capacity in ɑ-Ni(OH)2 makes it own the great potential to be applied in new generation of Ni-MH batteries.