Hydrothermal carbonization (HTC) of biomass such as glucose and cellulose typically produces micrometer-sized carbon spheres that are insulating. Adding a very small amount of Graphene oxide (GO) to glucose (e.g., 1:800 weight ratio) can significantly alter the morphology of its HTC product, resulting in more conductive carbon materials with higher degree of carbonization. At low mass loading level of GO, HTC treatment results in dispersed carbon platelets of tens of nanometers in thickness, while at high mass loading levels, free-standing carbon monoliths are obtained. Control experiments with other carbon materials such as graphite, carbon nanotubes, carbon black, and reduced GO show that only GO has significant effect in promoting HTC conversion, likely due to its good water processability, amphiphilicity, and two-dimensional structure that may help to template the initially carbonized materials. GO offers an additional advantage in that its graphene product can act as an in situ heating element to enable further carbonization of the HTC products very rapidly upon microwave irradiation. Similar effect of GO is also observed for the HTC treatment of cellulose.