Polyacrylonitrile (PAN) grafted amino-functionalized multi walled carbon nanotubes (amino-MWCNTs) were synthesized by in situ polymerization under aqueous solvent. The grafted MWCNT/PAN nascent composite fibers were prepared by the wet spinning method. Fourier transform infrared spectroscopy and Raman spectroscopy indicated that the amino-MWCNTs and PAN macromolecular chains had interfacial interactions and formed chemical bonds. The grafting content of the PAN polymer on the amino-MWCNTs was up to 73.2% by thermo gravimetric analysis. The incorporation of the grafted MWCNTs improved the degree of crystallization and crystal size of PAN nascent fibers, and changed the thermal properties during exothermic processing in an air atmosphere. Morphology analysis and testing of mechanical properties showed that the grafted MWCNT/PAN nascent composite fibers with a more uniform diameter distribution and larger diameter had higher tensile strength and tensile modulus than the control PAN nascent fibers.