In this work, a comparison of the performances of laser ablation-inductively coupled plasma mass spectrometry (LA-ICPMS) and portable X-ray fluorescence (XRF) spectrometry for the characterization of cobalt blue pigments used in the decoration of Valencian ceramics is presented. Qualitative data on the elemental composition of the blue pigments obtained using both techniques show a good agreement. Moreover, the results clearly illustrate that potters utilized different kinds of cobalt pigments in different historical periods. While both techniques seem suitable for the proposed task, they show different strengths and weaknesses. Portable X-ray fluorescence spectrometry is a cheaper and totally non-destructive technique, capable of providing fast and reliable results at the mgg(-1) level. LA-ICPMS, on the other hand, offers a much higher detection power and better spatial resolution, but its use results in some sample damage (sample consumption at the mug level), while it is a more expensive and non-portable technique.