Hypothesis: Pullulan, an exopolysaccharide consisting of maltotriose repeating units, has recently found many applications in different fields, such as food, packaging, cosmetics and pharmaceuticals. The introduction of photo-crosslinkable methacrylic units potentially allows to use pullulan derivative in inkjet 3D printing. Experiments: Pullulan was functionalized with methacrylic groups and the derivative was characterized by NMR, FT-IR and Raman spectroscopy. Water dispersions were thoroughly investigated by optical microscopy, SAXS and rheology to evaluate the self-assembly properties and they were used as photocrosslinkable inks in a 3D printer, also in comparison with pristine pullulan. The structural and mechanical properties of the obtained films were studied by Atomic Force Microscopy and tensile strength tests. Findings: The introduction of methacrylic groups moderately affects the self-assembly of the polymer in water, resulting in a slight increase of the gyration radius of the polymer coils and in a small decrease of the viscosity, retaining the typical shear-thinning behavior of concentrated polysaccharides in water. The structural and mechanical properties of the 3D printed films are much more affected, showing the presence of sub-micrometric phase segregated domains which are further separated by the cross-linking. As a result, the deformability of the materials is improved, with a lower tensile strength. Hypothesis: Pullulan, an exopolysaccharide consisting of maltotriose repeating units, has recently found many applications in different fields, such as food, packaging, cosmetics and pharmaceuticals. The intro-duction of photo-crosslinkable methacrylic units potentially allows to use pullulan derivative in inkjet 3D printing. Experiments: Pullulan was functionalized with methacrylic groups and the derivative was characterized by NMR, FT-IR and Raman spectroscopy. Water dispersions were thoroughly investigated by optical microscopy, SAXS and rheology to evaluate the self-assembly properties and they were used as photo-crosslinkable inks in a 3D printer, also in comparison with pristine pullulan. The structural and mechan-ical properties of the obtained films were studied by Atomic Force Microscopy and tensile strength tests. Findings: The introduction of methacrylic groups moderately affects the self-assembly of the polymer in water, resulting in a slight increase of the gyration radius of the polymer coils and in a small decrease of the viscosity, retaining the typical shear-thinning behavior of concentrated polysaccharides in water. The structural and mechanical properties of the 3D printed films are much more affected, showing the pres-ence of sub-micrometric phase segregated domains which are further separated by the cross-linking. As a result, the deformability of the materials is improved, with a lower tensile strength. (c) 2021 Elsevier Inc. All rights reserved.