CoFe2/CaO catalysts for multi-walled carbon nanotubes (MWCNT) were characterized during the activation period (T = 670 °C; C2H4/Ar = 1:1, 400 sccm) by internal field 59Co nuclear magnetic resonance. During this induction period, although C2H4 is already reacting, the MWCNT yield remains negligible. The NMR spectra of the catalysts revealed the occurrence of several structural and magnetic species. They were not detectable by conventional X-ray diffraction but the heterogeneity of the metal particles was corroborated by high-resolution transmission electronic microscopy coupled with energy dispersive X-ray spectroscopy. Two samples quenched at different activation time contained, beside non-reacted pure metal Co particles, strong and weak ferromagnetic alloys. During activation, the pure Co metal content dropped and an increase of the ordering of the cobalt-iron alloy in the catalyst was evidenced thus revealing a multistage activation mechanism for the reaction. We propose this ordering process during the induction period to be an intermediate step between the strong ferromagnetic Co rich alloy and the weak ferromagnetic Fe rich one and that it favors the onset of MWCNTs growth.