Piet Mondrian’s Broadway Boogie Woogie (1942–1943) was examined using Macro X-Ray Fluorescence mapping (MA-XRF) to help characterize the artist’s materials and understand his creative process as well as the current condition issues of the painting. The presence and distribution of key chemical elements was used to identify the main pigments in the different paint layers and under-layers, namely titanium white/barium sulfate, zinc white, bone black, cadmium yellow and/or cadmium-zinc yellow, cadmium red and/or cadmium-barium red and ultramarine. The XRF data was also examined using a multivariate curve resolution-alternating least square (MCR-ALS) approach to virtually separate and help characterize the different paint layers. Results suggest that Broadway Boogie Woogie was originally conceived as an asymmetrical grid of interlacing red and yellow bars. Mondrian then reworked the composition extensively breaking the bars by painting small squares in red, blue and gray and repainting them over and over again changing their size, color or tonality, and by adding and reworking large colored shapes in the background. Mondrian scraped off the paint in some areas before making adjustments to the composition but did not do it consistently throughout the painting. The yellow paint on the surface is severely cracked. Wherever red paint has been covered with yellow paint, it has oozed through the cracks in the top layer. The results illustrate how the MA-XRF / MCR-ALS approach can complement the examination of a painting and contribute to the understanding of the artist’s process and choice of materials in a non-invasive way.