Multiwalled carbon nanotubes (MWCNTs) were expanded by 2.5 times in diameter through high-energy (MeV) ion irradiation. Pristine MWCNTs were synthesized onto SiO2 substrate by chemical vapor deposition. The 4 MeV Cl2+ ions with a dose of 3×1016 ions/cm2 were irradiated on MWCNTs. From high-resolution transmission electron microscopy (HR-TEM) images, the average diameter of the high-energy-ion-irradiated MWCNTs was ∼180 nm, while that of the pristine MWCNTs was ∼70 nm. The wall thickness of the pristine and the high-energy-ion-irradiated MWCNT samples was ∼20 nm and 40–50 nm, respectively. We observed the clear formation of nanocompartments with bamboolike structure inside the tubes after ion irradiation. The amorphous carbon structure in the ion-irradiated MWCNT shells was observed from Raman spectra. Based on the results of HR-TEM and Raman spectra, the expansion of the systems represents morphological transition from crystalline graphite structure to amorphous carbon or finite sized graphite structure due to the ion impact. We suggest that high-energy ion irradiation can be useful for the modification of MWCNT structures.