Graphene-based composite materials are highly sought after for space applications due to their ability to encompass various properties, such as electrical conductivity, thermal resistance, and radiation shielding. This versatility allows for the creation of multifunctional components that can serve various purposes in space. Three-dimensional (3D) printing of composite materials in space offers a versatile and efficient means of manufacturing components, tools, and structures that are tailored to the unique challenges and requirements of space missions. In this work, we aim to develop 3D-printed composites made of medium-density polyethylene (MDPE) matrix and exfoliated graphene nanoplatelets (xGnP) as filler, using fused filament fabrication (FFF). Our research focuses on the challenges associated with the FFF process for fabricating MDPE/xGnP materials, particularly by optimizing filament extrusion and assessing the resulting material properties and space environmental compatibility. Firstly, we optimize the extrusion process, and use the MDPE/xGnP filaments to fabricate 3D-printed samples after defining the FFF parameters. We employ differential scanning calorimetry (DSC) to assess the melting properties and crystallization degree of the extruded filaments and 3D-printed samples, providing insights into the relationship between these properties and the characteristics of the initial powders. Electrical and tensile tests are carried out to evaluate the material properties after successfully mitigating challenges, such as warping and inadequate adhesion, to build plates during the printing process. Finally, we subject the 3D-printed composites to outgassing tests under exposure to the AM0 solar spectrum to evaluate their space environmental suitability. The results of this work demonstrate the capability of the FFF-based process to efficiently manufacture components made of MDPE/xGnP composites, providing optimized parameters for their potential in-space fabrication.