The photoinduced intramolecular charge separation (CS) and charge recombination (CR) phenomena in a series of donor-bridge-acceptor (D-B-A) molecules are intensively investigated as a means of understanding electron transport through the π-B. Pyrene (Pyr) and triarylamine (TAA) moieties connected via phenylene Bs of various lengths are studied because their CS and CR behaviors can be readily monitored in real time by femtosecond transient absorption (fs-TA) spectroscopy. By combining the steady-state and fs-TA spectroscopic measurements in a variety of solvents together with chemical calculations, the parameters that govern the CS behaviors of these dyads were obtained, such as the solvent effects on free energy and the B-length-dependent electronic coupling (VDA) between D and A. We observed the sharp switch of the CS behavior with the increase of the solvent polarity and B-linker lengths. Furthermore, in the case of the shortest distance between D and A when the electron coupling is sufficiently large, we observed that the CS phenomenon occurs even in low-polar solvents. Upon increasing the length of B, CS occurs only in strong polar solvents. The distance-dependent decay constant of the CS rate is determined as ∼0.53 Å-1, indicating that CS is governed by superexchange tunneling interactions. The CS rate constants are also approximately estimated using Marcus electron transfer theory, and the results imply that the VDA value is the key factor dominating the CS rate, while the facile rotation of the phenylene B is important for modulating the lifetime of the charge-separated state in these D-B-A dyads. These results shed light on the practical strategy for obtaining a high CS efficiency with a long-lived CS state in TAA-B-Pyr derivatives.