Attribution of the panel The Virgin with the Child and an Angel today in the Art Museum of Girona is under study due to the existence of two hypotheses, both of them not thoroughly documented, pointing Jan Massys and Bernardo Luini as potential authors. Attribution process is an important issue in many museums and collections. In this article, the question is addressed by combining material and iconographic information, paying special attention to the information yielded by minor components, and by following the material characteristics of the existing restoration interventions. In addition to imaging and classical analytical techniques (SEM and FTIR), the capability of a new developed Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry system for minor elements and thin layers detection is also discussed. Results confirmed a 16th century palette and revealed the use of specific pigments such as Verditer and Smalt. Analytical results combined with iconographic characteristics, permitted the contextualization of the painting in North Europe in the circle of production of Antwerp between 1500-1550. This conclusion does not allow the direct attribution to Jan Massys but minimize the probabilities of Bernadino Luini as author.