The use of nylon-6 electrospun nanofiber mats as reinforcement with synergistic effect in tensile strength and toughness for melamine-formaldehyde (MF) resin is highlighted in this article. Interestingly, there was a drastic effect of the wetting procedure of reinforcing fiber mat by the MF resin on the morphology and mechanical properties of the composites. The wetting of nylon fibers by passing through a solution of MF resin showed a core-shell morphology and a significant improvement in properties as compared to the dip-coating procedure for wetting of the fibers. Depending on the wt% of reinforcing nylon fiber mats, the composites could be considered as either fiber reinforced MF composites or MF glued nylon fibers.