A novel methodology is presented for the enhanced electrochemical detection of oleuropein in complex plant matrices by Graphene Oxide Pencil Grahite Electrode (GOPGE) in combination with a buffer modified with a Natural Deep Eutectic Solvent, containing 10% (v/v) of Lactic acid, Glucose and H2O (LGH). The electrochemical behavior of oleuropein in the modified-working buffer was examined using differential pulse voltammetry. The combination of both modifications, NADES modified buffer and nanomaterial modified electrode, LGH-GOPGE, resulted on a signal enhancement of 5.3 times higher than the bare electrode with unmodified buffer. A calibration curve of oleuropein was performed between 0.10 to 37 mu M and a good linearity was obtained with a correlation coefficient of 0.989. Detection and quantification limits of the method were obtained as 30 and 102 nM, respectively. In addition, precision studies indicated that the voltammetric method was sufficiently repeatable, %RSD 0.01 and 3.16 (n = 5) for potential and intensity, respectively. Finally, the proposed electrochemical sensor was successfully applied to the determination of oleuropein in an olive leaf extract prepared by ultrasound-assisted extraction. The results obtained with the proposed electrochemical sensor were compared with Capillary Zone Electrophoresis analysis with satisfactory results.