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Using ultrathin electrospun poly(methyl methacrylate) (PMMA) nanofibers as precursor, graphitic nanoribbons could be prepared by electron beam irradiation. With the help of the high resolution transmission electron microscopy, the real time processing of the carbonization and graphitization of the PMMA nanofibers could be clearly seen. By precisely controlling the irradiation, the graphitic nanoribbons could be fine-tuned. The mechanism of the transformation from PMMA to graphitic nanoribbons was analyzed detailedly. This new way to obtain graphitic nanoribbons from ultrathin electrospun PMMA nanofibers has promising potential applications in graphitic carbon nanostructure electronics and devices. Meanwhile, this carbonization and graphitization explained how PMMA could be inverted into negative electron resist from positive resist by high dose electron beam lithography, which provides a way to obtain patterned graphitic nanostructures directly from PMMA.