We fabricated a novel sensitive ferrocene end-cap polyester dendrimer (Fc-PED)- graphene oxide (GO) modified glassy carbon electrode (Fc-PED/GO/GCE) for direct quantification of Di(2-methoxyethyl) phthalate (DMEP) in liquor sample. GO sheets were bonded on the Fc-PED molecules by the chemical reaction between Fc-PED and GO sheets to form Fc-PED-GO composites. Construction of electrochemical sensors using the structure of nano-sized dendrimer will offer compact matrix for the incorporation of GO sheets, which provided more possibilities for the design of sensor to improve the film forming performance and the electrochemical activity of the electrode. GO sheet also provided a larger surface area to facilitate deposition of Fc-PED redox probe, which increased the current response of the modified sensor. The Fc-PED/GO/GCE sensor demonstrated a wide linear detection range of 0.06-1200 μmol.L−1with a low detection limit of 0.04μmol.L−1. Furthermore, the sensor showed higher sensitivity, good selectivity and reproducibility towards DMEP detection. The feasibility of the electrochemical sensor was proved by successful detection of DMEP in real liquor samples. Possible synergistic effect of Fc-PED and GO towards DMEP detection are proposed based on experimental results.