We report the first experimental observation of the D(2)(1)Pi state in the NaLi molecule. Polarisation labelling spectroscopy technique is applied to observe transitions to all vibrational levels in this state, save v = 0. The inverted perturbation approach method is used to construct a pointwise potential curve for the D state, which has a small barrier (9.3 cm(-1)) to dissociation, located at 7.98 angstrom. (C) 2013 Published by Elsevier B.V.