This paper presents the first insight into how Almada Negreiros, a key artist of the first generation of modernism in Portugal, created his mural painting masterpiece in the maritime station of Rocha do Conde de Óbidos in Lisbon. This set of six monumental mural paintings dates from 1946 to 1949 and is considered Almada’s artistic epitome. As part of the ALMADA project: Unveiling the mural painting art of Almada Negreiros, the murals are being analyzed from a technical and material perspective to understand his modus operandi and the material used. This is the first study of this nature carried out on site and in the laboratory using standard and more advanced imaging, non-invasive analysis, and microanalysis techniques. This article reports the results obtained with visual examination, technical photography in visible (Vis), visible raking (Vis-Rak), complemented by 2D and 3D optical microscopy (OM), scanning electron microscopy with energy-dispersive spectrometry (SEM-EDS), and Fourier transform infrared micro-spectroscopy (µ-FTIR) of the paint layers. The results show the similarities, differences, and technical difficulties that the painter may have had when working on the first, third, and presumably last mural to be painted. Vis-Rak light images were particularly useful in providing a clear idea of how the work progressed from top to bottom through large sections of plaster made with lime mortars. It also revealed an innovative pounced technique used by Almada Negreiros to transfer the drawings in full scale to the walls. Other technical characteristics highlighted by the analytical setup are the use of textured, opaque, and transparent paint layers. The structure of the paintings does not follow a rigid build-up from light to dark, showing that the artist freely adapted according to the motif represented. As far as the colour palette is concerned, Almada masterfully uses primary and complementary colours made with Fe-based pigments and with synthetic ultramarine blue, cadmium pigments, and emerald green.