Lubrication failure under heavy load condition due to the limited carrying capacity of base lubricants usually results in catastrophic failure of mechanical systems. In this work, a class of perfluorinated gel lubricants (PFGs) is prepared, retaining excellent lubricity and load-carrying performances under high load. Self-assembly mechanism confirmed by molecular dynamics simulation indicates that the gelators in PFGs self-assemble into a 3D network structure through intermolecular hydrogen bonds. The confinement effect of gelator self-assembly in the base oil contributes to avoiding lubrication failure and environmental pollution caused by base oil creeping and leakage. Simple synthesis, creep recovery, and high sol-gel phase transition temperatures confer more benefits for PFGs applications. Moreover, X-ray photoelectron spectroscopy and transmission electron microscopy techniques are employed to investigate the lubrication mechanism of PFGs, revealing that lubricants can interact with the friction interface to form two layers of tribofilm which are formed by adsorption and tribochemical reaction. PFGs provide an eco-friendly solution for lubricating under heavy load condition.