Engineered fiber reinforced polymer composites require effective impregnation of polymer matrix within the fibers to form coherent interfaces. In this work, we investigated solution interactions with electrospun fiber mats for the manufacture of nanocomposites with optimized mechanical properties. Void free composites of electrospun nonwoven PA6 nanofibers were manufactured using a PVA matrix that is introduced into the nonwoven mat using a solution-based processing method. The highest failure stress of the composites was reported for an optimum 16 wt % of PVA in solution, indicating the removal of voids in the composite as the PVA solution both impregnates the nanofiber network and fills all the pores of the network with PVA matrix upon evaporation of the solvent. These processing methods are effective for achieving coherent nanofiber-matrix interfaces, with further functionality demonstrated for optically transparent electrospun nanofiber composites.