Electrospinning at relatively low polymer concentrations results in particles rather than fibers. This particle-formation process can be termed as electrospray. So electrospinning/electrospray is a highly versatile method to process fibers and particles with different morphologies. In this work, poly(methyl methacrylate) (PMMA) micro- and nanostructures with different morphologies (fibers, spheres, cup-like, and ring-like) have been produced by a facile electrospinning/electrospray method. PMMA was electrospun into various morphologies from only DMF without any other solvents. Field emission scanning electron microscope (FESEM) images demonstrate the different morphologies and prove this technique to be an effective method for obtaining morphology-controllable polymer materials by changing the processing parameters. These micro- and nanostructured polymer materials may find applications in drug delivery and filtration media.