A series of catalysts, NiSO4/TiO2, for ethylene dimerization was prepared by the impregnation method using aqueous solution of nickel sulfate. On the basis of the results obtained from X-ray diffraction, the addition of NiSO4 shifted the transition of TiO2 from the anatase to the rutile phase toward higher temperatures due to the interaction between NiSO4 and TiO2. Nickel sulfate supported on titania was found to be very active even at room temperature. The high catalytic activity of NiSO4/TiO2 closely correlated with the increase of acidity and acid strength due to the addition of NiSO4. It is suggested that the active sites responsible for ethylene dimerization consist of low valent nickel, Ni+, with an acid.