Herein, we present the electrochemical co-deposition of Al3+/graphene composites directly from an aqueous mixture containing graphene oxide (GO) and Al3+. The obtained Al3+/graphene composites with good electrochemical activity were regarded as an appropriate immobilization platform for double-stranded DNA (dsDNA). The nontoxic redox probe xanthurenic acid (XA) was successfully applied to recognize single-stranded DNA and dsDNA. We illustrated that the scission of dsDNA caused by GO combining with some metal ions could be detected by monitoring the electrochemical signals of XA.