A range of substituted ferrocenes were used as catalysts for the synthesis of multi-walled carbon nanotubes (MWCNTs) and carbon fibers (CFs). These products were obtained in the temperature range 800–1000°C, in a reducing atmosphere of 5% H2 by pyrolysis of (CpR)(CpR′)Fe (R and R′=H, Me, Et and COMe) in toluene solution. The effect of pyrolysis temperature (800–1000°C), catalyst concentration (5 and 10wt.% in toluene) and solution injection rate (0.2 and 0.8ml/min) on the type and yield of carbonaceous product synthesized was investigated. Carbonaceous products formed include graphite film (mostly at high temperature; 900–1000°C), carbon nanotubes and carbon fibers. The carbonaceous materials were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Raman spectroscopy. The ferrocene ring substituents influenced both the CNT diameter and the carbon product formed.