Photon-induced fission has been investigated as a method to detect and identify nuclear materials. Although high-energy delayed-fission γ-rays have been considered as a reliable signature for detection of fissionable materials, interference from γ-rays produced as secondary effects from other photonuclear reactions is inevitable. This effect has been studied in distinguishing fissionable materials from non-fissionable materials based on differential delayed γ-ray yields via both simulation and measurements. The energy spectra of delayed-photofission γ-rays carry isotopic information of the target materials. The feasibility of accurate spectrometry measurements in between intense linear accelerator pulses has been demonstrated using three independent spectroscopy systems. The measured delayed γ-rays spectra were then compared with MCNPX simulation results. Through the comparison, this article intends to show the capabilities of the current version of MCNPX in applications of simulating the photofission process.