The majority of the photocatalysts studied for azo-dye degradation are based on semiconductor materials. Studies reported on non-semiconducting materials are very scarce. In the present work, we studied the fullerene (C60) ability to accelerate photodegradation of the dye’s azo bond in the presence of ascorbic acid. A series of C60 supported on ordered mesoporous silica (MCM-41) catalysts, containing 1, 3, 6, 9, and 12 wt % of fullerene C60, was studied using Orange G (OG) as representative azo-dye. This study showed that partial decolorization is achieved in the dark by simple adsorption of the dye on the bare surface of the carrier. The extent of decolorization increases with the irradiation of the suspension due to photocatalytic degradation of the azo-bond. This is maximized over the sample containing 3 wt % of C60 and it has been attributed to the best combination of the extent of the dye adsorption with the high intrinsic photocatalytic activity of small C60 clusters predominated in this sample. This catalyst proved to be quite stable upon five subsequent photocatalytic cycles, losing less than 5% of its initial activity. No degradation of OG takes place in the absence of ascorbic acid.