In this research, optically transparent composites were successfully fabricated by embedding polyacylonitrile hollow nanofibers into poly(methyl methacrylate) matrix. Hollow polyacylonitrile nanofibers were first prepared by coaxial electrospinning polyacylonitrile/mineral oil solution, followed by etching with octane to remove the mineral oil from the fibers. Polyacylonitrile hollow fibers were then homogeneously distributed in poly(methyl methacrylate) resins to fabricate the composite. The embedded polyacylonitrile hollow nanofibers significantly enhanced the tensile stress and the Young’s modulus of the composite (increased by 58.3% and 50.4%, respectively), while having little influence on the light transmittance of the composite. This novel transparent composite could be used for transparent armor protection, window panes in vehicles and buildings, airplane windshield, etc.