The picosecond excited-state dynamics of several derivatives have been investigated using high photon energy excitation combined with picosecond luminescence detection. Instrument response-limited fluorescence (τ(1) ≈ 3-5 ps) at 500 nm was observed for all of the complexes, while longer-lived emission (τ(2) > 50 ps), similar in energy, was observed for only some of the complexes. Interestingly, the presence of τ(2) required substitution at the 4,4-positions of the bipyridine ligands and D-3 symmetry for the complex; only the 4,4-substituted homoleptic complexes exhibited τ(2). On the basis of previous assignments of the ultrafast dynamics measured for Ru(bpy)(3)(2+) and Ru(dmb)(3)(2+), τ(2) has been tentatively ascribed to relaxation from higher electronic or vibrational levels in the triplet Manifold having slightly more triplet character than the state responsible for τ(1). However, given that the kinetics for these transition metal complexes are highly dependent on both pump and probe wavelengths and that there is considerable interest in utilizing such complexes for electron transfer in the nonergodic limit, further characterization of the state giving rise to τ(2) is warranted.