The metal–organic framework (MOF) HKUST‐1 was employed as an interaction matrix for fundamental loading studies of anthraquinone dyes. Chosen dyes were alizarin (A), alizarin S (AS), disperse blue 1 (B1), disperse blue 3 (B3), disperse blue 56 (B56) and purpurin (P). All materials were characterized by XRD, FTIR, TGA and SEM. Hence the interaction of dyes with the framework was characterized by theoretical–experimental differential analysis. One‐pot loading strategy resulted in more efficient scavenging of dyes, and reached 100 % for B56 using 50 mg L−1. SEM revealed important microstructural changes, the smaller crystals ranged 0.8–3 μm in size and almost all composite sizes were from this to higher values, reaching 70 μm, with varying shapes. Two composites were larger in size range (about 2500–1000 μm), and were shaped as rods, octahedrons and coffin lids. Indeed, the microstructure could be modulated depending on preparation conditions and type of loaded dye. For the higher loading series, N2 adsorption and XPS experiments were carried on to further evidence dye–MOF interactions. Ab initio prediction of structural properties for A@HKUST‐1 and P@HKUST‐1 were obtained by means of solid‐state CRYSTAL14 code at the PBE0 level of theory. Computed findings evidenced two O→Cu coordinative bonds, one from O‐ketone and the other from O‐phenolate moiety as main interactions towards CuNET centers. The dye is cast: The metal–organic framework (MOF) HKUST‐1 was employed as an interaction matrix for fundamental loading studies of anthraquinone dyes (e.g., alizarin in the picture). The interaction of dyes with the framework was characterized by theoretical–experimental differential analysis. A microstructural changes were encountered.