Five highly excited (1)Sigma(+)(g) states of Na(2) were observed for the first time by pulsed optical-optical double resonance (OODR) fluorescence excitation spectroscopy. Three of the five states are assigned to the 6svarsigma (1)Sigma(+)(g), 6dvarsigma (1)Sigma(+)(g), and 7dvarsigma (1)Sigma(+)(g) Rydberg states. The other two states are assigned to doubly excited (1)Sigma(+)(g) states. Copyright 1999 Academic Press.