During the seventeenth century, the use of smalt and indigo became increasingly common among painters’ workshops in New Spain. The unprecedented importance of these two blue pigments in oil painting may be explained by artistic and geopolitical circumstances. This article expands on the use of blue smalt—a byproduct of glass production and a material that lacks in-depth study in viceregal painting—by focusing on the technical analysis of El Triunfo de la Eucaristía and La Asunción painted by Cristóbal de Villalpando (ca. 1649–1714), which are part of the collection of the Museo Regional de Guadalajara (Mexico). The technological and material study of both paintings, situated within the trade and circulation of painting materials at the turn of the eighteenth century, shows how the painter deployed techniques rooted in his predecessors while incorporating particular technical adaptations. The authors examine cross-section samples of Villalpando’s paintings with optical microscopy, Scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDX), and Fourier-transformed infrared spectroscopy (FT-IR), and were able to identify different qualities of smalt as well to suggest a possible provenance. These analyses evidence novel aspects in the painting tradition of workshops in New Spain that ultimately reverberated in practices of the long eighteenth century.