We have observed the 5 (1)Pi(u), 6 (1)Sigma(u)(+), and 7 (1)Sigma(u)(+) states of Na-2 by using all-optical triple resonance excitation and an ultrasensitive shielded cylindrical space-charge-limited ionization detector (presumably detecting Na-3(+) produced by Na-2* + Na associative ionization). Although the absolute vibrational numbering is uncertain, the rotational constants are obtained,The Franck-Condon window concept is presented with calculated Franck-Condon factors based on the theoretical 5 (1)Pi(u), 6 (1)Sigma(u)(+), and 7 (1)Sigma(u)(+) potential energy curves of Magnier.