A multistep laser excitation scheme was used to access the last, least bound levels close to the lowest asymptote
3s+3s with the molecular states $X{}^{1}{\ensuremath{\Sigma}}_{g}^{+}$ and $a{}^{3}{\ensuremath{\Sigma}}_{u}^{+}$ of
Na2. All singlet levels within the last $10 {\mathrm{cm}}^{\ensuremath{-}1}$, and some triplet levels with sufficient singlet admixture, were observed. The level energies were determined with uncertainties of less than 22 MHz with respect to the dissociation limit. The hyperfine structure was resolved, and asymmetric line shapes due to predissociation by tunneling through the rotational barrier or electronic state coupling were recorded for levels above the dissociation limit.