The overexposure process of poly(methyl methacrylate) (PMMA) was studied in detail using electron-beam lithography. It was found that PMMA films could be directly patterned without development due to the electron-beam-induced collapse of PMMA macromolecular chains. By analyzing the evolution of surface morphologies and compositions of the overexposed PMMA films, it was also found that the transformation of PMMA from positive to negative resist was a carbonization process, so patterned carbonaceous nanostructures could be prepared directly by overexposure of PMMA using electron-beam lithography. This simple one-step process for directly obtaining patterned carbonaceous nanostructures has promising potential application as a tool to make masks and templates, nanoelectrodes, and building blocks for MEMS and nanophotonic devices.