Two dimensional (2D) nanomaterials with high gravimetric capacity and rate capability are a key strategy for the anode of a Li-ion battery, but they still pose a challenge for Li-ion storage due to limited conductivity and an inability to alleviate the volume change upon lithiation and delithiation. In this paper, we report the construction of a 3D architecture anode consisting of exfoliated 2D layered graphitic carbon nitride (g-C3N4) and reduced graphene oxide (rGO) nanosheets (CN-rGO) by hydrothermal synthesis. First, bulk g-C3N4 is converted to nanosheets to increase the edge density of the inert basal planes since the edges act as active Li-storage sites. This unique 3D architecture, which consists of ultrathin g-C3N4 nanosheets sandwiched between conductive rGO networks, exhibits a capacity of 970mAhg−1 after 300 cycles, which is 15 fold higher than the bulk g-C3N4. The tuning of the intrinsic structural properties of bulk g-C3N4 by this simple bottom-up synthesis has rendered a 3D architectured material (CN-rGO) as an effective negative electrode for high energy storage applications.