This investigation is focused on the identification in ceramic artworks of certain nonstandard yellow/orange pigments whose composition is based, fundamentally, on lead, tin, and antimony oxides with or without silica. In this work, a comparative study (temporal and geographical) of the employment of these yellow pigments in different production centers, from Italy (Pesaro and Montelupo) and Spain (Talavera de la Reina), during the Renaissance and Baroque epochs has been proposed. For this purpose, special very ancient yellow pigments were acquired from the Stazione Sperimentale del Vetro, Murano-Venezia (Italy). These reference pigments have been produced following strict and rigorous manufacturing recipes corresponding to Venezian fabrication processes for the 16th and 17th centuries. On the other hand, the portable characteristic of a new optical fiber Raman system has allowed us the access into the Museo de Cerámica de Barcelona in order to investigate the composition of the yellow and orange colors of an important ceramic collection belonging to this museum. The results are in good agreement with the ones obtained by other authors who have investigated the same topic. It is notable, first, the excellent performances that this portable Raman system offers in the direct and non-invasive analysis of ceramic artworks and, second, the coincidences of the molecular results among these yellow pigments. This fact confirms that these pigments were commonly used either in Italian and Spanish ceramic objects during both Renaissance and Baroque epochs. Copyright © 2012 John Wiley & Sons, Ltd.