The development of self-healing polymeric materials is gaining increasing interest in the aerospace field, particularly for lunar exploration missions. Spacecraft and equipment operating on the Moon are continuously exposed to extreme conditions, including micrometeoroid impacts and abrasive lunar dust, which can cause surface damage over time. This work focuses on the fabrication and characterization of polyimide-based materials with intrinsic self-healing properties and shape memory functions. To ensure a more sustainable approach, a bio-based solvent, dimethyl isosorbide (DMI), was used for the synthesis of the poly(amic) acids, which were subsequently imidized by thermal treatment. Traditionally, the synthesis of these polymers relies on solvents that are toxic to both human health and the environment. Our chemical approach involves replacing these hazardous solvents with greener alternatives. The aim is to achieve material properties and performance similar to or better than those obtained with traditional solvents, ensuring suitability for use in space environments. To enhance the self-repairing ability, boric acid (BA) was incorporated into the polymer matrix, enabling healing through strong hydrogen bonding interactions. Additionally, the introduction of trifluoromethyl groups improved flexibility and mechanical performance. Structural and surface characterizations confirmed the successful synthesis and functional properties of the membranes. Additionally, shape memory behavior was demonstrated, allowing the material to autonomously recover its original form. The findings suggest that these polyimide materials have great potential for extending the durability of space structures, minimizing maintenance efforts, and improving mission reliability.