Polarisation labelling spectroscopy has been used to record the excitation spectrum of KLi in the region 18 500 to 20800 cm(-1). Transitions are observed to all bound levels of the D(1)Pi state, and to some high vibrational levels of the C(1)Sigma(+) state, both of which dissociate to K(4S) + Li(2P) atoms. Spectroscopic constants are given for both electronic states. A pointwise potential curve is constructed for the D(1)Pi state, which has a small barrier (26.5 cm(-1)) to dissociation, located at 7.79 Angstrom. (C) 2003 Elsevier Science B.V. All rights reserved.