The phase composition and comparison of iron-based catalysts used for the synthesis of carbon nanotubes were investigated. This work reflects typical catalyst conditions and their evolution during the growth of carbon nanotubes. The preparation of carbon nanotubes was carried out by chemical vapour deposition at temperatures between 800 and 1100 °C. Ferrocene or zero-valent iron nanoparticles were used as “catalysts”, and toluene, ferrocene and the ferrocene–toluene solution played the role of carbon precursors, respectively. The phase composition of the prepared product was studied by Mössbauer spectroscopy and X-ray powder diffraction. Mössbauer analysis was particularly useful for samples with a low content of the nanoparticle form of the catalyst. The composition of the prepared samples differed depending on the synthesis temperature, catalyst and precursor. Phase analysis revealed the presence of α-Fe and Fe3C in all samples. In addition, γ-Fe and iron oxides were identified under certain conditions. Scanning and transmission electron microscopy confirmed the carbon nanotube/nanofibre-like morphology and the presence of iron species.