High yield and quality mutli-walled carbon nanotube (MWNT) bundles and carbon nanofibers were synthesized by catalytic decomposition of methane over Co/MgMoO4 catalyst at 1 000 ℃. TEM studies showed that the products were mainly carbon nanofibers without carrier gas and were all MWNT bundles with hydrogen or nitrogen as carrier gas. Thermal gravimetric analyses (TGA) on the raw product indicated that the purity of MWNT was higher than 95wt%. The growth mechanism of carbon nanofibers and MWNTs was also discussed.