An electrospinning process was used to fabricate poly(methyl methacrylate) (PMMA) nanofibers embedding multi-walled carbon nanotubes (MWNTs). SEM images showed that the nanofiber surface and structural morphology depended on solvent types (dimethyl formamide, chloroform and toluene) and carbon nanotube contents (0.5 and 3.0 wt%). Nanofiber alignments could be controlled by adjusting the electrodes configuration at collector sites. Relationship between carbon nanotube and PMMA nanofiber was studied with radius of gyration of polymer chain and carbon nanotube sizes. As the carbon nanotube content ratio increased, the number of bead increased.