The photo-induced luminescence properties of Egyptian blue, Han blue and Han purple were investigated by means of near-infrared digital imaging. These pigments emit infrared radiation when excited in the visible range. The emission can be recorded by means of a modified commercial digital camera equipped with suitable glass filters. A variety of visible light sources were investigated to test their ability to excite luminescence in the pigments. Light-emitting diodes, which do not emit stray infrared radiation, proved an excellent source for the excitation of luminescence in all three compounds. In general, the use of visible radiation emitters with low emission in the infrared range allowed the presence of the pigments to be determined and their distribution to be spatially resolved. This qualitative imaging technique can be easily applied in situ for a rapid characterisation of materials. The results were compared to those for Egyptian green and for historical and modern blue pigments. Examples of the application of the technique on polychrome works of art are presented.