Heterogeneous catalysis is a promising method in industry to synthesis bioactive molecules, fine chemicals and pharmaceuticals. Particularly, cross-coupling reactions using transition metal catalyst are the hot topic of research in recent period due to its efficiency. Nanofibers are most preferred for this purpose due to its huge surface area, easy separation and minimum catalyst loading. Herein, we are reporting palladium oxide nanofibers (PdO NF) of 75 nm, prepared by electrospinning technique, as catalyst for the cross-coupling of challenging bromo, chloro and fluoro benzonitriles. The successfulness of the present catalytic system was evidenced from the coupling products (confirmed by H-1 & C-13 NMR) of the most reluctant fluoro benzonitriles. Furthermore, possible mechanism for the rapid formation was proposed based on the products and literature reports. In addition to the above, heterogeneity and metal leaching was verified (by GC-MS and ICP-MS) with the aim to scale up the process.