A self-constructed Geant4 Monte Carlo simulation has been built to simulate time-of-flight (TOF) measurement for 236U accelerator mass spectrometry (AMS). Time resolution of experiment in 9.4 and 2 ug/cm2 of carbon foil cases are 2.633 ns and 1.853 ns, respectively. Time resolution of Geant4 simulation in 9.4 and 2 ug/cm2 of carbon foil cases are 1.997 ns and 1.379 ns, respectively. The results show a good agreement between Geant4 simulation and experiment at two different thickness of carbon foil cases. The results of Geant4 simulation and experiment show this TOF detection system has an ultrasensitivity in timing measurement.