The findings of this study show the initial feasibility of electrospun nanofibers in improving the compressive behaviors of hardened cement pastes. Electrospun nylon nanofibers and two modified versions of them with single-walled carbon nanotubes and micro-silica particles are fabricated and integrated directly into cement (nylon fibers, SWCNT-nylon fibers, and McSi-nylon fibers). Toughness and compressive strength of materials are considered to investigate the change in the compressive behaviors of the pastes. The findings showed an increase of 63.2% in toughness when modified cement paste with the McSi-nylon fibers, while increases of 24 and 22.1% are observed when adding nylon and SWCNT-nylon fibers into the cement pastes, respectively. In addition, an increase of 36.4% is observed in compressive strength in the sample containing McSi-nylon fibers while the others show almost unchanged results. Besides, field emission scanning electron microscopy (FE–SEM), and thermal gravimetric analysis (TGA) are conducted to investigate the change in the inner structure of the cement matrix and can be reasonable explanations for the change in the mechanical strength. Based on the findings of the present study, the initial potential of hybrid electrospun nanofiber in improving the compressive performance of cementitious materials is clarified.