N2 is a diatomic molecule with complex electronic structure. Interstate crossings are prominent in the high energy domain, introducing significant perturbations to the system. Nitrogen mainly photodissociates in the vacuum ultraviolet (VUV) region of the electromagnetic spectrum through both direct and indirect predissociation. Due to the complexity introduced by these perturbations, the nitrogen isotopic fractionation in N2 photodissociation is extremely hard to calculate, and an experimental approach is required. Here we present new data of N-isotopic fractionation in N2 photodissociation at low temperature (80 K), which shows a distinctly different 15N enrichment profile compared to that at relatively higher temperatures (200 and 300 K). The new data, important to understanding the N-isotopic compositions measured in meteorites and other planetary bodies, are discussed in light of the knowledge of N2 photochemistry and calculated photoabsorption cross sections in the VUV.