In this study, we report the preparation and comparison of the rosin based thin films and electrospun fibers in terms of their formation and characterizations. Rosin in the form of thin films and fibers can be obtained via wet casting method and electrospinning process, respectively. Systematic experiments were performed to study the morphology, structure and thermal properties of the rosin thin films and electrospun fibers. Finally, in order to understand the accurate mass values of rosin in the different morphologies, we performed matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF) spectroscopy. The rosin thin film prepared via wet casting method exhibited very smooth surfaces whereas the electrospun fibers were continuous without any beads over long distances. The MALDI-TOF data revealed that the most intense peak in the molecular weight of rosin components is about 302 for the rosin powder, thin film and fibers. On the other hand, some of the higher molecular component can also be observed for electrospun rosin fibers owing to the structural morphology. The present study demonstrated that the full structural characterization of the molecular species present in these different forms of rosin.