TiO2 fibers were prepared through electrospinning of poly methyl methacrylate (PMMA) and titanium isopropoxide (TIP) solution followed by calcination of fibers in air at 500 degrees C. Cetyltrimethylammonium bromide (CTAB) protected palladium nanoparticles (Pd NPs) prepared through reduction method were successfully adsorbed on the TiO2 nanofibers (NF). Combined studies of X-ray diffraction (XRD), scanning electron microscope (SEM), and transmission electron microscope (TEM) indicated that the synthesized Pd/TiO2 had anatase. BET indicated that the synthesized TiO2 and Pd/TiO2 had a surface area of 53.4 and 43.4m(2)/g, respectively. The activity and selectivity of 1 mol% Pd/TiO2 in the Heck reaction have been investigated towards the Mizoroki-Heck carbon-carbon cross-coupling of bromobenzene (ArBr) and styrene. Temperature, time, solvent, and base were optimized and catalyst was recycled thrice. H-1 NMR and C-13 NMR indicated that stilbene, a known compound from literature, was obtained in various Heck reactions at temperatures between 100 degrees C and 140 degrees C but the recyclability was limited due to some palladium leaching and catalyst poisoning which probably arose from some residual carbon from the polymer. The catalyst was found to be highly active under air atmosphere with reaction temperatures up to 140 degrees C. Optimized reaction condition resulted in 89.7% conversions with a TON of 1993.4 and TOF value of 332.2 hr(-1).