The singly excited Ca(4s4d pi(3)D(J)).AT((3) Pi(0-)), and Ca(4s4d delta(3)D(J)).Ar((3) Delta(1)) valence states and the unusual doubly excited Ca(4p pi 4p pi P-3(J)).Ar((3) Sigma(-)) valence state have been characterized via Resonance Enhanced Two-Photon Ionization (R2PI) spectroscopy of transitions from the long-lived Ca(4s4p pi P-3(J)).Ar((3) Pi(0-)) metastable state of the CaAr van der Waals molecule. Because the Ar atom can approach along the nodal axis of the quite diffuse Ca(4d delta) orbital with little repulsion, the CaAr(4s4d delta (3) Delta(1)) state is fairly strongly bound (D-0 = 609+/-50 cm(-1)) , but less bound than the CaAr+ ''core'' ion (D-0= 775+/-50 cm(-1)). The CaAr(il 4s4d pi (3) Pi(0-)) state is less bound (D-0-450 +/- 50 cm(-1)), but has a bond strength much greater than that of the lower-energy CaAr(4s4p pi 3 Pi(0-)) state (D-0= 60 +/- 50 cm(-1)). The doubly excited CaAr(4p pi 4p pi (3) Sigma(-)) State is extremely strongly bound (D-0= 1277 +/- 50 cm(-1)), and this is attributed to the lack of a valence Ca(4s) electron. The Ar atom can therefore approach with minimal repulsion along the nodal axes of the two transversely aligned Ca(4p pi) electrons. The Ca(4p pi 4p pi (3) Sigma(-)) State is also strongly predissociated, with a lifetime less than 10 ps. (C) 1997 American Institute of Physics.