Taking advantages of short pulse excitation and time-resolved photoluminescence (PL), we have studied the exciton localization effect in a number of GaAsN alloys and GaAsN/GaAs quantum wells (QWs). In the PL spectra, an extra transition located at the higher energy side of the commonly reported N-related emissions is observed. By measuring PL dependence on temperature and excitation power along with PL dynamics study, the new PL peak has been identified as a transition of the band edge-related recombination in dilute GaAsN alloy and delocalized transition in QWs. Using selective excitation PL we further attribute the localized emission in QWs to the excitons localized at the GaAsN/GaAs interfaces. This interface-related exciton localization could be greatly reduced by a rapid thermal annealing.