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Hybrid multiscale fiber reinforced epoxy composite laminates were developed and characterized from woven glass fiber mats reinforced with nonwoven PAN nanofibers (diameters of 200 nm) produced via electrospinning. An electrospinning setup was designed and developed to produce continuous E‐spun nonwoven nanofiber (NWNF) mats, which were then used as interlaminar reinforcements for producing multiscale hybrid composites. A detailed study for producing E‐spun nanomats considering both solution and operation parameters was undertaken discussed and optimum spinning parameters were obtained. These parameters were used to produce the E‐spun NWNF mats, which were inserted into the interlaminar region of glass fiber reinforced epoxy laminates. The impact absorption energy, tensile strength, and flexural strength of the hybrid multiscale composites were found to increase with an increase in E‐spun NWNF mat weight fraction. These properties were compared to those of a conventional glass fiber composite laminates prepared from the neat epoxy resin with 32% glass fiber volume fraction. The effectiveness of the strengthening/toughening strategy formulated in this study indicates that the feasibility of using the E‐spun NWNF mat reinforcements for improving the mechanical properties of structured high‐performance composites. In addition, the present study provides motivation for the long‐term development of high‐strength high toughness bulk structural nanocomposites for broader engineering applications. [ABSTRACT FROM AUTHOR]