AbstractThe ever‐increasing demand for additive manufacturing (AM) is driven by the technology's rapid prototyping and flexible manufacturing benefits. Among the various AM techniques, fused filament fabrication (FFF) is one of the most commonly used techniques, in which thermoplastic polymer filaments are deposited layer by layer to create the final part. This technique has been used extensively in various sectors. However, new materials have yet to be developed for use in FFF. This research aims to introduce a new biodegradable highly amorphous polyvinyl alcohol (HAVOH), commercially known as G‐Polymer (GP), into the scope of FFF, to propose a process window for the fabrication of parts with enhanced mechanical properties and to discover the process‐structure–property relationship for this material. This study investigates the effect of five key parameters in GP FFF, including raster angle, number of contours, nozzle temperature, build platform temperature, and print speed. The results of the chemical, thermal, and thermo‐mechanical analysis of the filaments before and after hot extrusion of the 3D printer nozzle showed a significant increase in the mechanical properties of the hot‐extruded filaments. In addition, the mechanical characterization of 3D printed parts showed that increasing the number of contours can improve the mechanical properties of parts, while the raster angle can have a complex effect. The mechanical properties of the parts are also improved by reducing the temperature of the nozzle and the build platform. Printing speed, as an essential parameter in AM, was related to the previously mentioned parameters, and the results showed that increasing the printing speed could improve the UTS and Young's modulus of the 3D printed part.Highlights A novel biodegradable polymer (HAVOH) was introduced into the scope of FFF. The hot extruded G‐Polymer filament from the nozzle showed improved mechanical properties. 180°C nozzle and room temperature platform resulted in improved mechanical properties. 3D printed parts with +45°/−45° raster angle show improved mechanical properties 110 mm/s print speed results in higher mechanical strength than 70 mm/s print speed.