The sol-gel technique has been studied to fabricate a homogeneous Fe-Mo/MgO catalyst. Ambient effects (air, Ar, and H2) on thermal decomposition of the citrate precursor have been systematically investigated to fabricate an Fe-Mo/MgO catalyst. Severe agglomeration of metal catalyst was observed under thermal decomposition of citrate precursor in air atmosphere. Ar/H2 atmosphere effectively restricted agglomeration of bimetallic catalyst and formation of highly-dispersed Fe-Mo/MgO catalyst with high specific surface-area due to the formation of Fe-Mo nanoclusters within MgO support. High-quality thin-multiwalled carbon nanotubes (t-MWCNTs) with uniform diameters were achieved on a large scale by catalytic decomposition of methane over Fe-Mo/MgO catalyst prepared under Ar-atmosphere. The produced t-MWCNTs had outer diameters in the range of 4-8 nm (average diameter ~6.6 nm) and wall numbers in the range of 4-7 graphenes. The as-synthesized t-MWCNTs showed product yields over 450% relative to the utilized Fe-Mo/MgO catalyst, and indicated a purity of about 85%.