Application of a voltage ramp can result in denaturation of dsDNA and strand separation. We show that the potential at which half of the surface immobilised duplexes denature (the melting potential, E(m)) directly correlates with the calculated nearest neighbour and experimental melting temperatures; T(m), for a duplex is solution. The results demonstrate that the electrochemical melting potential measures the stability of the dsDNA, and therefore existing nearest neighbour melting models can be utilized to design DNA probes with predictable electrochemical melting potentials for future assay applications.