Despite recent progress in 3D printing of graphene, formulation of aqueous 3D printable graphene inks with desired rheological properties for direct ink writing (DIW) of multifunctional graphene macrostructures remains a major challenge. In this work, we develop a novel 3D printable pristine graphene ink in aqueous phase using conductive nanofibrillar network formulation by controlling the interfacial interactions between graphene and PEDOT:PSS nanofibrils. The formulated inks, tailored for energy applications, provide excellent 3D printability for fabricating multilayer 3D structures (up to 30 layers) with spanning features and high aspect ratio. The 3D printed aerogels, comprising interconnected networks of graphene flakes and PEDOT:PSS nanofibrils, exhibit excellent electrical conductivity as high as ∼630 S m − 1 and can be converted into conductive hydrogels via swelling in water/electrolyte. The formulated graphene inks were used for fabricating 3D printed supercapacitor electrodes (power density of 11.3 kW kg−1 and energy density of 7.3 Wh kg−1) with excellent performance and durability.