The improvement of the mechanical properties of concrete can be achieved with the use of synthetic macrofibers. However, this fiber–matrix interaction will be sufficiently efficient for tensile efforts only when there is a binding agent that associates the characteristics of the paste with the characteristics of the surface of the reinforcing material. As already identified, in a first phase of this research using synthetic microfibers, a better fiber–matrix interaction can be achieved with the surface treatment of synthetic fibers with graphene oxide. In this way, we sought to evaluate the surface treatment with graphene oxide on two synthetic polypropylene macrofibers (macrofiber “A” and macrofiber “B”) and its contribution to the concrete transition zone. The surface deposition on the macrofiber was carried out using the ultrasonication method; then, the macrofiber with the best deposition for creating reinforced concrete mixtures was identified. To evaluate the quality of GO deposition, scanning electron microscopy (SEM-FEG) and energy-dispersive spectroscopy (EDS) tests were carried out; the same technique was used to evaluate the macrofiber–matrix transition zone. The SEM-FEG images indicated that macrofiber “B” obtained greater homogeneity in surface deposition and it presented a 13% greater deposition of C in the EDS spectra. The SEM-FEG micrographs for reinforced concrete indicated a reduction in voids in the macrofiber–matrix transition zone for concretes that used macrofibers treated with GO.