The optical Kerr effect exhibited by a nickel doped zinc oxide thin solid film was explored with femto- and pico-second pulses using the z-scan method. The samples were prepared by the ultrasonic spray pyrolysis technique. Opposite signs for the value of the nonlinear refractive index were observed in the two experiments. Self-defocusing together with a two-photon absorption process was observed with 120 ps pulses at 1064 nm, while a dominantly self-focusing effect accompanied by saturated absorption was found for 80 fs pulses at 825 nm. Regarding the nanostructured morphology of the resulting film, we attribute the difference in the two ultrafast optical responses to the different physical mechanism responsible of energy transfer generated by multiphoton processes under electronic and thermal effects.