In the current work, palladium nanoparticles (Pd NPs) were prepared from palladium acetate biogenically using the aqueous-ethanolic extract of black pepper (Piper nigrum) and characterized by various analytical techniques like XRD, FE-SEM, EDS, TEM, ATR-IR, UV-Vis spectroscopy, BET, TGA and ICP-OES analysis. The reduction of Pd(II) to Pd(0) is achieved by the action of various phytochemicals present in the black pepper extract like phenols, acids, pellitorine, ethyl piperonyl cyanoacetate, piperine and N-isobutyl-tetradeca-2,4-dienamide. The biosynthesized Pd NPs shown excellent catalytic activity in aryl halide cyanation and Hiyama cross-coupling reactions. Also, less toxic potassium hexacyanoferrate(II) trihydrate was used as cyanide source in aryl halide cyanation and Hiyama cross-coupling was performed under fluoride free condition. Both reactions proceeded well with Pd NPs under ligand free circumstances to give good to excellent yields. The Pd NPs were recovered after each reaction and recycled up to five times in aryl halide cyanation and ten times in Hiyama cross-coupling without considerable loss in the activity. Green synthesis of palladium nanoparticles: applications in aryl halide cyanation and Hiyama cross-coupling reaction under ligand free conditions. [GRAPHICS] .