Multistitched three-dimensional (3D) woven E-glass/polyester/nanosilica composite (MNS) was developed. Its mechanical and impact performances were characterized for particular end-use applications. It was found that the warp-weft directional tensile strength and modulus of MNS structure were higher than those of the off-axis directions. In addition, there was not a big difference between warp and weft directional bending and short beam strengths of MNS structure. The MNS structure had a small damaged area under low velocity impact load. The failure was confined at a narrow area because of multistitching and nanomaterial and resulted in the catastrophic fiber breakages in the normal direction of the applied load of the structure. The results from the study indicated that the multistitching and the addition of nanosilica in the composite structure improved its damage tolerance.