All-aromatic polyimides serve as versatile precursors for carbon formation due to their high aromatic content and repeating unit planarity, which synergistically enables pyrolysis to ordered carbon. Recent publications disclosed facile synthetic methods for additive manufacturing (3D printing) of all-aromatic polyimides using a pendant salt approach for ultraviolet-assisted direct ink write (DIW) additive manufacturing. This manuscript describes the introduction of pendant sodium sulfonate functionality to the poly(amic acids), and water-soluble all-aromatic polyimide precursors displayed suitable rheological properties for DIW at room temperature and vat photopolymerization (VP) at 50 °C. These aqueous solutions enabled the formation of microporous polyimide structures with a direct freeze-casting method and dense structures with gradual heating under inert atmosphere to 200 °C and subsequent thermal post-processing to 400 °C. Furthermore, polyimide 3D structures function as efficient carbon precursors when pyrolyzed at 2000 °C under inert atmosphere. Raman spectroscopy revealed carbonized 3D structures with characteristic graphitic and disordered carbon bands, which was indicative of polycrystalline, disordered glassy carbon. Furthermore, electrical conductivity measurements suggest opportunities for the formation of 3D conductive structures.