This study reports the acquisition of molecular rolling lubrication by self-curling of graphite nanosheets (GNSs) at cryogenic temperature. The edge self-curling nanodeformation phenomenon of GNSs at 77 K is used to promote the formation of graphite nanorollers in the friction process, leading to molecular rolling lubrication. The observation of parallel nanorollers at the friction interface provides experimental evidence for molecular rolling lubrication, and graphite exhibits abnormal lubrication performance in vacuum with ultra-low friction and wear at macroscale. The molecular rolling lubrication mechanism is elucidated from the electronic interaction perspective. Experiments and theoretical simulations indicate that the driving force of the self-curling is the uneven atomic shrinkage induced stress, and then the shear force promotes the intact nanoroller formation, while the constraint of atomic vibration decreases the dissipation of driving stress and favors the nanoroller formation. This study opens up a new pathway for controlling friction at microscale and nanostructural manipulation. The research demonstrates that cryogenic temperature can induce the self-curling of GNSs, leading to the formation of nanorollers that function as molecular bearings, achieving ultra-low friction and wear in vacuum. The study also reveals that the suppression of atomic vibration at cryogenic temperature favors the formation of nanorollers. The molecular rolling lubrication mechanism is explained through density functional theory (DFT) simulations, showing that the rolling process has significantly lower energy dissipation compared to sliding. This work provides the first conclusive experimental evidence for the occurrence of molecular rolling lubrication and its contribution to macroscale low friction, offering a universal principle for overcoming the failure problem in extreme environments of existing layered lubricant systems. The study has implications for the control of friction and nanostructural manipulation in various fields.This study reports the acquisition of molecular rolling lubrication by self-curling of graphite nanosheets (GNSs) at cryogenic temperature. The edge self-curling nanodeformation phenomenon of GNSs at 77 K is used to promote the formation of graphite nanorollers in the friction process, leading to molecular rolling lubrication. The observation of parallel nanorollers at the friction interface provides experimental evidence for molecular rolling lubrication, and graphite exhibits abnormal lubrication performance in vacuum with ultra-low friction and wear at macroscale. The molecular rolling lubrication mechanism is elucidated from the electronic interaction perspective. Experiments and theoretical simulations indicate that the driving force of the self-curling is the uneven atomic shrinkage induced stress, and then the shear force promotes the intact nanoroller formation, while the constraint of atomic vibration decreases the dissipation of driving stress and favors the nanoroller formation. This study opens up a new pathway for controlling friction at microscale and nanostructural manipulation. The research demonstrates that cryogenic temperature can induce the self-curling of GNSs, leading to the formation of nanorollers that function as molecular bearings, achieving ultra-low friction and wear in vacuum. The study also reveals that the suppression of atomic vibration at cryogenic temperature favors the formation of nanorollers. The molecular rolling lubrication mechanism is explained through density functional theory (DFT) simulations, showing that the rolling process has significantly lower energy dissipation compared to sliding. This work provides the first conclusive experimental evidence for the occurrence of molecular rolling lubrication and its contribution to macroscale low friction, offering a universal principle for overcoming the failure problem in extreme environments of existing layered lubricant systems. The study has implications for the control of friction and nanostructural manipulation in various fields.