The lowest E1((3)Sigma(+)) Rydberg state of the CdNe van der Waals complex was investigated by an optical-optical double resonance method. The A0(+)((3)Pi) and B1((3)Sigma(+)) states were used as intermediates in the excitation from the X0(+)((1)Sigma(-)) ground state. Bound-bound excitation spectra of the E1 - A0(+) transition were recorded. They constitute a first observation of CdNe in the E1-state. Spectroscopical parameters of the E1-state potential well were determined. In the excitation spectrum of the E1 - B1 transition, a nodal structure of bound-free transitions was observed and elucidated by a projection of the B1-state vibrational wave-function onto the E1-state potential barrier according to the prediction of ab initio calculations. (C) 2002 Published by Elsevier Science B.V.