This study presents the feasibility of improving some selected mechanical strengths and the inner-structural analyses of cement matrix by electrospun nanofibers containing nylon 66, nanosilica, and carbon nanotube. The hybrid electrospun nanofibers were fabricated and mixed into ordinary Portland cement. From the mechanical strength test results, the hybrid nanofibers have shown their role in improving the tensile, compressive, and toughness behavior of the mixed cement material. The improvements of 62%, 38%, and 69%, respectively, were observed compared to those of the control paste. The novelty of the surface and inner structure of the hybrid fibers, as well as the modified cement matrix, were observed by the scanned images from electron microscopes. Besides, the additional pozzolanic reaction between the generated calcium hydroxide and the attached silica was clarified thanks to the results of energy dispersive spectroscopy, X-ray diffraction, and thermal gravimetric analysis. Finally, the consistency between mechanical strength results and inner-structure analyses showed the potential of the proposed fiber to improve cement-based materials.