The kinetic parameters for the chemical reaction of nano-NiO of different particle sizes with aqueous sodium bisulfate solution were determined; additionally, the influence of particle size on the kinetic parameters were studied and were discussed. The results show that: there are clear effects of the particle size of nano-NiO on the rate constant, the reaction order, the apparent activation energy and the pre-exponential factor; thus the rate constant and the reaction order increase, and the apparent activation energy and the pre-exponential factor decrease, with decrease of the particle diameter; the logarithm of the preexponential factor, and the apparent activation energy, exhibit a linear relationship with the reciprocal of the particle diameter respectively. The bases of the role of the particle size are that the reaction order is influenced by the molar surface area of nano-NiO, the apparent activation energy by the molar surface energy, the preexponential factor by the molar surface entropy, and the rate constant by both the molar surface energy and the molar surface entropy.