Compared to enzymatic glucose sensors, non-enzymatic glucose sensors offer significant advantages in sensitivity, stability, and cost. In this study, a green and simple electrochemical method was employed to prepare an electrochemical non-enzymatic glucose sensor based on graphene/PEDOT/Ni materials. The modified electrode was characterized using scanning electron microscopy (SEM), Raman spectroscopy, Fourier-transform infrared spectroscopy (FTIR), cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS). The electrochemical behavior of glucose on the modified electrode was investigated, and the results indicated that the sensor exhibited a good electrochemical response to glucose. Experimental conditions were optimized, and under the optimal conditions, the sensor showed a good linear relationship with glucose concentration in the range of 0.0001 to 7 mM, with a detection limit of 0.012 μM. The sensitivity was 1561 μA·mM−1·cm−2, demonstrating excellent reliability, stability, and accuracy.