Abstract The dispersion of multi-walled carbon nanotubes (MWNTs) in crystalline poly(ethylene oxide) (PEO) is significantly improved by grafting with poly(methyl methacrylate) (PMMA) on surface of MWNTs via emulsion reactions. The synthesized MWNTs-g-PMMA is soluble in solvents that can dissolve PMMA and is well dispersed in PEO. The effects of the MWNTs-g-PMMA on PEO crystallization and its use as a reinforcement for PEO are investigated using DMA, DSC, POM, and SAXS. DMA data show that the PEO/MWNTs-g-PMMA blends containing up to 30 wt% MWNTs-g-PMMA are compatible. DSC data show the crystallization of PEO is enhanced by the MWNTs-g-PMMA, accompanying with a decreased thickness of crystal layers and an increased thickness of amorphous layers of the PEO lamellar stacks, in combination with SAXS data.