The evolution of the microstructure and mechanical properties of electrodeposited nanocrystalline Ni with different annealing procedures was studied systematically. For the annealed specimens hardness decreases with increasing average grain size but the dependence changes at different grain size ranges. The specimens annealed at a low temperature show higher hardness compared to the as-deposited nanocrystalline Ni, despite an increased measured average grain size. In association with this hardening an increase in elastic modulus and a decrease in microstrain was observed after annealing. With increasing annealing temperature both the tensile strength and the fracture strain were observed to decrease, this is companied with a transition from ductile to brittle in the fracture surfaces. These results indicated that the mechanical behaviour of nanocrystalline Ni depends not only on the average grain size but also on the grain boundary structure. A change in the grain boundary state arising from annealing may be responsible for the observed increase in hardness and elastic modulus as well as the deterioration of tensile properties.