Newly designed push-pull ligands (L1 and L2) with bithiophene (bth) as a donor and phenazine (phz) or quinoxalino[2,3-b]quinoxaline (qxq) as acceptors were synthesized and also incorporated with a bipyridyl Ru(II) complex to give Ru1 and Ru2, respectively. The ultrafast photophysical dynamics of the ligand and their respective Ru(II) complexes were well-characterized using time-resolved spectroscopies and quantum chemical calculations. Photoinduced charger transfer (CT) and intersystem crossing (ISC) processes were directly observed for L1 and L2. In addition, the interplay of three different triplet excited states was directly observed in the related Ru(II) complexes. The lowest-lying triplet excited states of the ligands and their respective Ru(II) complexes were both attributed to the CT transitions from donor (bth) to acceptor (phz or qxq) and result in 3ICT (intramolecular charge transfer) and 3ILCT (intraligand charge transfer) excited states, respectively. The lifetimes of the lowest-lying triplet excited states of L1, L2, Ru1, and Ru2 were measured to be 21.3, 50.4, 2.75, and 4.16 μs, respectively.