A study of the effects of nano-silica treatment on the bonding properties of macro synthetic polypropylene fibers embedded in a cement matrix is provided in the present paper as a step to improve interfacial properties of the fiber reinforced cementitious composites (FRCC). Polypropylene fibers were treated by sol–gel technique, allowing to obtain a nano-silica coating. Scanning electron microscopy was used to observe the morphological features of PP fibers surfaces before and after the pullout test. The effects of the treatment were investigated by comparative pullout tests on treated and untreated fibers. An increase in maximum load and energy necessary for the complete extraction of the fiber was observed, as a consequence of the improvement of the interface properties due to the nano-silica hydration activity. These two parameters control the crack-resistance and ductility properties of FRCC and are deeply influenced by bonding and friction phenomena. The hydration products act as chemical and physical anchors, thus producing a densification of the interface transition zone (ITZ). The abrasion phenomena occurring on the fiber surface during the pullout test are responsible of hardening behavior, consisting in the increase in the frictional shear stress with the fiber slip and thus in the energy required for fiber extraction.