The mechanical deformation processes of poly(methyl methacrylate)/ montmorillonite nanocomposites and their electrospun fibers were investigated by in situ tensile tests under a transmission electron microscope depending on their morphology. While the polymer nanocomposites deformed in a brittle manner, i.e., crazing, the electrospun polymer nanocomposite fibers deformed through a shear flow process leading to "nanoneeking" due to the strong overlap of stress fields caused by nanopores within the fiber under a uniaxial tensile load. This unique change in deformation behavior provides the possibility that the intrinsic brittle material could be manipulated to be ductile without sacrificing its other attractive properties through a well-controlled electrospinning process.