Deexcitation energies of superdeformed secondary minima of odd-odd Au and Tl isotopes are investigatedwith the relativistic mean field (RMF) model where the isoscalar-isovector coupling is included to change the symmetryenergy.It is verified by the theoretical analysis and numerical results that the deexcitation energies of superdeformedsecondary minima relative to the ground states in these heavy nuclei are sensitive to differences in the symmetry energy.In particular, the linear correlation between the deexcitation energies of odd-odd Au and Tl isotopes and the neutron skinthickness in 208Pb is established.Moreover, explorations are extended to superdeformed candidates of other mass regions.It is found that the linear correlation can even be established between the deexcitation energies and the symmetry pressureat subsaturation density.These indicate that deexcitation energies can serve as a probe to the density dependence ofthe symmetry energy.