The defect distributions have been investigated using positron lifetime spectroscopy on amorphous and nanocrystalline Pr2Fe14B samples, produced by melt-spinning and nanocrystallization route. The main two components can be concluded that were ascribed to vacancy-like defects in the intergranular layers or the interfaces, and microvoids or large free volumes with size compared to several missing atoms at the interactions of the atomic aggregates or the crystallites. The remarkable changes in the positron lifetimes from the amorphous structure to the nanocrystalline with varied sizes can be interpreted, indicating that the structural transformation and the grain growth induce the defect distribution changes occurring at the interfaces with different shape and size.