Developing advanced polymer composites for defense applications requires sustainable manufacturing methods that deliver both structural strength and multifunctionality. This research explores the use of Multi-Material Direct Ink Writing (MDIW) to fabricate high-performance composites based on biodegradable polyvinyl alcohol (PVA) and carbon materials. MDIW enables precise spatial control over material deposition, allowing for the creation of complex architectures with tailored mechanical and functional properties. By integrating carbon-based fillers into the PVA matrix, we enhance the composite’s mechanical strength, thermal stability, and electrical conductivity—critical attributes for defense uses such as lightweight armor, structural supports, and embedded sensing components. The use of biodegradable PVA offers an environmentally responsible alternative to traditional petroleum-based polymers, aligning with growing sustainability goals in defense materials development. This study demonstrates the potential of MDIW in producing eco-friendly, high-performance composites, offering a scalable and versatile approach to next-generation defense technologies.