Concurrent electrocatalysis and sensing of hydrazine, sulfite ions, and nitrite ions in a mixture were studied using electrodes modified by electrodeposited Au nanostructures (NSs). The β-cyclodextrin-mixed silicate sol-gel composite was dropcasted on the electrode surface and nucleation guided by β-cyclodextrin occurred, followed by the electrodeposition of Au NSs. The additive, β-cyclodextrin, played an evident role as a structure-directing agent; thus, small raspberry-like Au NSs were obtained. The modified electrodes were characterized by surface characterization techniques and electrochemical methods. The Au NSs-modified electrodes effciently electrocatalyzed the oxidation of toxic molecules such as hydrazine and sulfite and nitrite ions even in the absence of any other electron transfer mediator or enzyme immobilization. Wellresolved oxidation peaks along with decreased overpotentials were noticed during the electrooxidation process. The fabricated Au nanostructured electrode clearly distinguished the electrooxidation peaks of each of the three analytes from their mixture.