The aim of this work was to elaborate the 3D printed polylactide (PLA) polymeric scaffolds and, subsequently, study the possibility of coating thereof with a biomedical polyvinylpyrrolidone (PVP) hydrogel through the previously patented protocol. Such materials have a potential to be applied in biomedical engineering, e.g. for tissue regeneration. PVP layer according to the present paper could constitute a useful biocompatible supporting layer for drug delivering implant surfaces of any shape. Polylactide (PLA) both in forms of flat foils and 3D-printed scaffolds was used to be coated with PVP layer with the Fenton-type reaction that enables the polymeric scaffold grafting with hydrogel in two easy steps. The study revealed that PVP was successfully grafted to PLA substrates. Most optimal parameters for PVP grafting process were selected. The PLA-PVP materials were found to be hydrophilic and non-toxic which is promising considering their biomedical application. The method comprising well-tested PLA scaffolds printing and then grafting them with PVP layer has a promising potential to be brought in to the industrial production due to its simplicity.