Sunflower is a widely cultivated oilseed, and its oil presents high nutritional quality and economic value. The objective of this work was to use pulsed electric fields pre-treatment in sunflower seeds to obtain higher oil extraction yields and higher extraction kinetics of the process. Electrical treatments were carried out with different input electric fields up to 7 kV/cm. Evaluation of treatment efficiency was performed through the analysis of the diffusion coefficient, disintegration index of the seeds and oil yield. The disintegration index increased with the energy input. PEF pre-treatment increased the oil yield by 8.1%. The extraction kinetics was studied on the basis of Fick’s diffusion equation. Comparing analysis showed that diffusion coefficient increased from D = 9.8943E−12 to 1.5504E−11 m2/s for untreated and treated samples subsequently. Kinetic parameters PEF pre-treatment extraction can be used for intensification processes in industry scale.