Photons with energy totaling more than 10 MeV provide efficient treatment for deeply seated tumors but interact with the nuclei of high-Z materials constituting a head of the linac. These interactions result in photoneutrons that deliver an additional out-of-field dose to the patient, which increases the risk of radiation-induced cancer. Monte Carlo simulation is an accurate strategy for estimating the effective photoneutron dose for a patient. In the current study, the possibility of using GEANT4 to calculate the photoneutron spectrum from the medical linac was investigated. The free-in-air photoneutron spectrum from a head of the linac was simulated using the NeutronHP experimental package. Validation of the simulated model was carried out based on a comparison of simulated and measured percentage depth–dose curves from photons in the water phantom. The obtained photoneutron spectrum was compared with the previously measured spectrum at the Varian Thilogy linac. GEANT4 may improve the accuracy of calculations of the effective dose based on photoneutrons. However, the simulated model should be improved and optimized. In the future, this model may constitute a physical basis for the prediction of the risk of radiation-induced cancer at our clinical center.