The development of Al-Ni alloys with a controlled microstructure has had a great impact on the field of study of aluminum-based alloys. In the present research, the influence of thermal parameters on the grain structures resulting from the directional solidification process of Al-Ni alloys with different alloy content has been studied. It has also been evaluated how different structures and the distribution of second phases influence the corrosion behavior and microhardness of alloys. The columnar-to-equiaxed transition (CET) was observed to occur when the temperature gradient in the melt decreased to values between 1.3 and 2.9 °C/cm. In addition, a small increase in the microhardness values was observed as a function of the Ni content. When the Ni content increases, the resistance to polarization decreases for samples with equiaxed grain structure throughout the range of compositions studied. Furthermore, the equiaxed grain structure presents higher resistance to polarization values than the columnar grain zone for alloys with a composition equal to or lower than the eutectic composition.