Sintered coatings of cordierite-base glass-ceramic do not adhere readily on bare molybdenum substrates. This is due to the absence of a stable metal oxide film on the substrate that serves as a suitable transition layer between the glass-ceramic and the substrate. To address this problem, dual layers of either chromium/nickel or chromium/copper were deposited by electroplating on the molybdenum substrates. Glass powder in slurry form was then cast on the substrates using a doctor blade and sintered in a helium-hydrogen atmosphere at 950°C. The metallic interlayer structure was found to produce an excellent bond between the coating and the substrate. The adhesion of the coatings was observed to be sensitive to the thickness of the deposited metal layers. Quantitative chemical analysis of the interface region was performed to explain the difference in adhesion quality. In all instances, the fracture surface was found to occur at the chromium oxide/chromium boundary providing a clear indication that the chromium oxide layer plays an important role in enhancing the adhesion. The superior adhesion in samples with the Cr-Cu interface was attributed to Cu acting as an effective diffusion barrier to Mo. Cr however, was able to diffuse through the Cu layer enhancing the bond between Mo and Cu by alloying with the Mo. Ni was not as effective as Cu in preventing the diffusion of Mo towards the glass-ceramic coating but a thicker Cr layer still produced a strong bond. In samples where the distinct Cr layer was either too thin or non-existent, adhesion was poor possibly because the Cr oxide does not bond well to the Ni-Cr alloy layer that formed after firing.