Strengthened nanofiber-reinforced epoxy matrix composites are demonstrated by engineering composite electrospun fibers of multi-walled carbon nanotubes (MWCNTs) and reactive P(St-co-GMA). MWCNTs are incorporated into surface-modified, reactive P(St-co-GMA) nanofibers by electrospinning; functionalization of these MWCNT/P(St-co-GMA) composite nanofibers with epoxide moieties facilitates bonding at the interface of the cross linked fibers and the epoxy matrix, effectively reinforcing and toughening the epoxy resin. Rheological properties are determined and thermodynamic stabilization is demonstrated for MWCNTs in the P(St-co-GMA)-DMF polymer solution. Homogeneity and uniformity of the fiber formation within the electrospun mats are achieved at polymer concentration of 30 wt %. Results show that the MWCNT fraction decreases the polymer solution viscosity, yielding a narrower fiber diameter. The fiber diameter drops from an average of 630 nm to 460 nm, as the MWCNTs wt fraction (1, 1.5, and 2%) is increased. The electrospun nanofibers of the MWCNTs/P(St-co-GMA) composite are also embedded into an epoxy resin to investigate their reinforcing abilities. A significant increase in the mechanical response is observed, up to >20% in flexural modulus, when compared to neat epoxy, despite a very low composite fiber weight fraction (at about 0.2% by a single-layer fibrous mat). The increase is attributed to the combined effect of the two factors the inherent strength of the well-dispersed MWCNTs and the surface chemistry of the electrospun fibers that have been modified with epoxide to enable, cross linking between the polymer matrix and the nanofibers.