The paper reports the first results of observing the visible photoluminescence from the surface of tantalum silicide samples subjected to electrochemical anodization in HF-containing electrolyte. It is shown that at increased concentrations of HF (more than 20%) and low current densities uniform dissolution of the silicide film takes place. A lower HF concentration (10%) yields the same effect at low current densities, whereas higher currents result in formation of a porous passive anodic layer composed of silicon dioxide with small inclusions of elemental silicon and tantalum oxide. These passive layers are efficiently luminescent.