Micro-Raman spectroscopy and the laser-induced transformation technique were used for systematic study of five coloured glazes on Saint John the Baptist (29 inch tondo), a majolica terracotta relief attributed to Luca Della Robbia and on permanent exhibit in The John and Mable Ringling Museum of Art. We suggest that S 3 − ions in a lead silicate matrix, called 'lead ultramarine', could contribute to the famous Della Robbia blue colour, in addition to the effect of Co atoms as suggested previously by Pappalardo et al. (2004). The original yellow glaze contains lead(II) antimonate. The green is a mixture of the yellow and blue pigments, the brown contains hematite, and the white glaze contains tin dioxide as an opacifier. The use of lead oxide as a main fluxing agent is confirmed by laser-induced micro-crystallization. KEYWORDS : MICRO-RAMAN SPECTROSCOPY, MAJOLICA GLAZES, ULTRAMARINE, PIGMENTS, RENAISSANCE, DELLA ROBBIA Figure 5 Representative Raman spectra of (I) the white glaze (the inset shows the extended spectral range of the same spectrum) and (II) cassiterite powder (Aldrich).