Herein We present, electrodeposition of gold dendritic nanostructures (Au-DNs) at reduced graphene oxide (RGO) functionalized with beta-cyclodextrins (CD). The structural features of the Au-DNs and their interfacing mechanism with RGO are characterized by UV-Visible, FESEM, EDX, XPS, XRD and Raman analysis. The growth mechanism of Au-DNs at RGO-CD support has been elucidated using FESEM measurements. The CD induces the formation and plays a crucial role in shaping the dendrite morphology of Au nanostructures at RGO-CD along with the ad layer of ammine functionalized silicate sol-gel matrix (TPDT). The combined effect of RGO and Au-DNs provoked the synergistic electrocatalytic activity towards the nitrite and glucose electrooxidation. (C) 2016 Published by Elsevier B.V.