The weakly bound complex Ca+-Ne is produced by laser ablation in a pulsed nozzle cluster source and low-lying electronic states are studied with resonance enhanced photodissociation spectroscopy (REPD). The lowest band system correlates to the forbidden D-2 <--S-2 atomic transition. Sharp structure to the blue of this transition is assigned to the C (2)Sigma(+)<-- X (2)Sigma(+) system. A vibrational progression (omega(e)(＇)=21.5 cm(-1)) and its convergence limit determine the excited-state dissociation energy of D-0(＇)=64 +/- 5 cm(-1). Two electronic systems in the complex are derived from the P-2 <--S-2 atomic transition. A doublet progression to the red of the atomic transition is assigned to the D (2)Pi(r)<-- X (2)Sigma(+) system. Extrapolation of the vibrational progression (omega(e)(＇)=134.5 cm(-1)) determines an excited-state dissociation energy of D-0(＇)=875 +/- 100 cm(-1). A broad continuum to the blue of the atomic transition is assigned to the E (2)Sigma(+)<-- X (2)Sigma(+) transition. Using the C (2)Sigma(+) excited-state convergence limit, the X (2)Sigma(+) ground-state dissociation energy is determined to be D-0(＇)=103 +/- 5 cm(-1). Rotational analyses from bands in both systems produce a ground-state bond length of r(0)(＇)=3.77 +/- 0.05 A. (C) 2000 American Institute of Physics. [S0021-9606(00)00610-3].