Mankind's quest for progress has led to the constant evolution of technologies that shape our lives. Among these, 3D printing, or additive manufacturing, stands out. 3D printing, also known as additive manufacturing, has revolutionized the way objects are designed and manufactured. This technology enables the creation of three-dimensional objects by layering materials based on digital models. With applications spanning from prototyping and manufacturing to medicine and art, 3D printing offers unparalleled customization, efficiency, and innovation. Its impact is profound in fields such as aerospace, automotive, healthcare, and consumer goods, where it reduces costs, accelerates production timelines, and allows for complex geometries that traditional manufacturing methods cannot achieve. This innovation has given rise to 4D printing, an enhanced version that responds dynamically to stimuli. Applicable across industries, these techniques address challenges while opening new possibilities. This approach overcomes traditional production constraints by utilizing advanced materials like smart polymers, carbon nanotubes, and graphene, yielding products adaptable to changing conditions. Out of various materials, polymer-graphene nanocomposites have emerged as a transformative technology in the realm of 3D and 4D printing. This chapter enlarges and encapsulates the fundamental synergy between graphene and polymers, showcasing their potential in additive manufacturing. The integration of graphene, with its remarkable mechanical, thermal, and electrical properties, enhances the performance of printed structures. The chapter explores the design and technical possibilities inherent in the combination of these materials, with a focus on both 3D and advanced 4D printing techniques. This innovative approach paves the way for functional and adaptable materials, offering unprecedented opportunities in various fields, from materials science to biotechnology. These advancements promise to reshape manufacturing capabilities and unlock novel applications, revolutionizing the landscape of printed structures and devices.