The present paper describes the effect of co-catalyst on the growth of multiwall carbon nanotube (MWCNT) by chemical vapor deposition (CVD) technique. The fascinating properties of CNT make them a suitable material for optoelectronic devices such as sensors, LED, solar cell, and field emission displays. MWCNTs were fabricated using CVD, by decomposing ethanol over finely dispersed Co metal as a catalyst at 750 °C. The effects of growth condition on the quality and morphology of MWCNTs were investigated by SEM, FTIR and XRD. SEM photographs show that the nanotubes are densely packed having a diameter of 10–15 nm. The bandgap was calculated by UV–visible spectroscopy and it was found varying from 3.08 to 3.5 eV by changing the substrates. The average size of tubes (length) was found to be 250 nm. FTIR exhibited that the synthesized MWCNTs were semiconducting in nature with the oxygen vacancies causing the variations in refractive index with the exposure of moisture.