Designing ultrathick and hierarchical electrodes is effective to deal with the challenge of high areal capacity and high power density for lithium-ion batteries (LIBs) manufacturing. Here, a thick electrode with hierarchical porous and multidimensional conductive network is fabricated by 3D printing technology, in which both the conducting polymer of poly(3,4-ethylene dioxythiophene):polystyrene sulfonate (PEDOT:PSS) and graphene oxide (GO) play the dual roles as binders and conductive agents. As a consequence, the 3D-printed thick electrode (∼900 μm) with a mass loading of ∼47 mg/cm2 exhibits a good rate capability of 122 mA·h/g at 2 C, a high areal capacity of up to 5.8 mA·h/cm2, and stable cycling performance of ∼95% capacity retention after 100 cycles. Moreover, the C-O-S bond is further confirmed by the spectral analysis and the DFT calculation, which not only hinders the stack of nanosheets but enhances the mechanical stability and electronic conductivity of electrodes. A stable covalent multidimensional conductive network constructed by 3D-printing technology provides a new design strategy to improve the performance of LIBs.