We report a novel boiling heat transfer (NBHT) in reduced graphene oxide (RGO) suspended in water (RGO colloid) near critical heat flux (CHF), which is traditionally the dangerous limitation of nucleate boiling heat transfer because of heater failure. When the heat flux reaches the maximum value (CHF) in RGO colloid pool boiling, the wall temperature increases gradually and slowly with an almost constant heat flux, contrary to the rapid wall temperature increase found during water pool boiling. The gained time by NBHT would provide the safer margin of the heat transfer and the amazing impact on the thermal system as the first report of graphene application. In addition, the CHF and boiling heat transfer performance also increase. This novel boiling phenomenon can effectively prevent heater failure because of the role played by the self-assembled three-dimensional foam-like graphene network (SFG).