Six early portraits from 1895 to 1900/1 by Pablo Picasso were comprehensively examined using complementary non-destructive techniques provided by the MOLAB Transnational Access Service as part of the European Cultural Heritage Advanced Research Infrastructures (CHARISMA) project. The paintings were selected by the Museu Picasso, Barcelona, as representative of Picasso's formative years. This paper presents a compendium of the results from the extensive analysis campaign, which involved meticulous inspection of the stratigraphy of each portrait and elucidation of the palette used by the artist in his early career. Subsurface imaging (X-ray radiography and infrared reflectography) was used to guide analytical data interpretation. Prussian blue, cobalt blue, ivory black, lead white, natural earths, vermilion, chromium-based pigments, and different fillers were identified in the paintings. With this simple palette, Picasso was able to play with the colors to create different shades and tones. Careful inspection of the brushstrokes and material distribution highlighted important details, providing a better understanding of the creative process behind the portraits studied and young Picasso's modus operandi. Furthermore, all the portraits were found to have been painted over earlier compositions.