This study aims to investigate the relationship between the steel fibers and the electromagnetic wave shielding effectiveness of a high-performance fiber-reinforced cementitious composite (HPFRCC). The distribution characteristics of the steel fibers and the variation of the electrical conductivity of HPFRCC as a function of the fiber content were quantified based on micro computed tomography (CT) and impedance measurements to determine their correlations with the electromagnetic shielding effectiveness. The impedance results showed that no electrical network was formed in the composite by the steel fibers and it is difficult to manufacture HPFRCC with high-electrical conductivity using steel fibers alone without CNTs or other carbon-based materials. For the steel fiber content of greater than 0.5%, the number of contact points between the steel fibers increased significantly, and the relationship between the fiber content and the number of contact points was observed. Despite the improvement of the electrical conductivity owing to the presence of the steel fibers and to the increase in the contact points between the steel fibers, the shielding effectiveness did not increase further for the steel fiber contents equal or above 1.5%. Consequently, it was found that the factor that controls the shielding effectiveness of HPFRCC is not the electrical network of the steel fibers, but the degree of the dispersion of the individual steel fibers.