Synthetic strategies for the improvement in electronic conductivities and electrochemical stabilities of transition metal oxide cathodes, which are limiting factors in the performance of commercial intercalation batteries, are required for next-generation, high-performance battery systems. The chemical preintercalation approach, consisting of a combined sequence of a sol–gel process, extended aging, and a hydrothermal treatment, is a versatile, wet synthesis technique that allows for the incorporation of a polar species between the layers of transition metal oxides. Here, formation of a layered 2D δ-CxV2O5·nH2O heterostructure occurs via chemical preintercalation of dopamine molecules between bilayers of vanadium oxide followed by the hydrothermal treatment of the precipitate, leading to carbonization of the organic molecules. The presence of carbon layers within the structure has been confirmed via a combined analysis of scanning electron microscopy, X-ray diffraction, thermogravimetric analysis, Raman spectroscopy, X-ray photoelectron spectroscopy, electrochemical impedance spectroscopy, four-probe conductivity measurements, and scanning transmission electron microscopy characterization. 2D δ-CxV2O5·nH2O heterostructure electrodes demonstrated significantly improved electrochemical performance, particularly at higher current densities, in Li-ion cells. The heterostructure electrodes exhibited 75% of the capacity retention when the current was changed from 20 mA g–1 (206 mAh g–1) to 300 mA g–1 (155 mAh g–1), while the reference δ-V2O5·nH2O electrodes exhibited only 10% capacity retention in the same experiment. Remarkably, 2D δ-CxV2O5·nH2O heterostructure electrodes demonstrated significantly improved capacity retention (94% after 30 cycles) for bilayered vanadium oxide electrodes in Li-ion cells during galvanostatic cycling at 20 mA g–1. The improved electrochemical performance, in both extended cycling and rate capability studies, of the 2D δ-CxV2O5·nH2O heterostructure electrodes in the Li-ion system is ascribed to the intermittent formation of carbon layers within the bilayered structure, which leads to increased electronic conductivity and improved structural stability of the heterostructure compared to the reference δ-V2O5·nH2O electrodes.