The results of the temperature dependence in fluid solution of the emission behavior of a series of [Re(L-L)(CO)(3)py](+) complexes (L-L = 3,4,7,8-Me(4)phen, 4,7-Ph(2)phen, 2,9-Me(2)-4,7-Ph(2)phen, 4,7-Me(2)phen, 5,6-Me(2)phen, 5-Phphen, 2,9-Me(2)phen, and phen) are presented along with an interpretation which assigns the lowest excited state as (3)MLCT, with a contribution from a higher-energy, shorter-lived state of unknown character. The emission lifetime of [Re(3,4,7,8-Me(4)phen)(CO)(3)py](+) actually increases with temperature, reaches a maximum at approximately 230 K, and then decreases in the usual manner. This behavior is attributed to population of the lowest (3)LC state, which in this complex lies just above the 3MLCT emitting state and below the upper state.