In this study, the effects of Nb on the microstructural characteristics, hardness, and corrosion resistance of high-silicon ductile cast iron (HSDI)-3.6 wt.% Si were investigated. Samples from different castings with 0–0.9 wt.% Nb were obtained and compared to a commercial ductile iron. Microstructures showed that the amount of ferrite in the matrix increased with increasing Nb content, from 34% for unalloyed HSDI to 88% for HSDI-0.9 wt.% Nb. The presence of randomly distributed NbC carbides was identified by EDX for all the samples alloyed with Nb, and the hardness of the HSDI increased with the Nb content. To evaluate the influence of the Nb content on the corrosion resistance of HSDI, potentiodynamic tests were carried out in a solution of H2SO4. The highest corrosion rate on HSDI was obtained for the HSDI-0.3 wt.% Nb sample, with 2802 mills per year, due to the amount of pearlite present and the lowest presence of NbC carbides, compared to the HSDI-0.9 wt.% Nb, with 986 mills per year. This behavior was attributed to the ferrite matrix obtained because of a high Si content in the DI, which delayed the anodic dissolution of the alloy and suppressed the pearlitizing effect of Nb for contents greater than 0.3 wt.%, as well as to the effect of NbC carbides, which acted as inhibitors.