Fluorescence spectroscopy and femtosecond relaxation dynamics of 2-{[2-(2-hydroxyphenyl)benzo[d]oxazol-6-yl]methylene)}malononitrile (diCN-MBO) and 2-{[2-(2-hydroxyphenyl)benzo[d]thiazol-6-yl]methylene}malononitrile (diCN-HBT) are Studied to probe the excited-state proton transfer (ESPT) Coupled charge transfer (ESCT) reaction. Unlike most of the ESPT/ESCT systems previously designed, in which ESCT takes place prior to ESPT. both diCN-HBO and diCN-HBT undergo ESPT. concomitantly accompanied with the charge transfer process, such that the ESPT reaction dynamics are directly Coupled with solvent polarization effects. The long-range solvent polarization interactions result in a solvent-induced barrier that affects the overall proton transfer reaction rate. In cyclohexane, the rate constant of ESPT of diCN-HBO is Measured to be 1.1 ps (9.1 x 10(11) s(-1)), which is apparently Slower than that of 150 fs for the parent molecule 2-(2'-hydroxyphenyl)benzoxazole (HBO). Upon increasing solvent polarity to, for example, CH3CN, the rate of ESPT is increased to 300 fs (3.3 x 10(12) s(-1)). The results are rationalized by the stabilization of proton transfer tautomer, which possesses a large degree of charge transfer character via an increase of the solvent polarity, such that the corresponding solvent-induced barrier is reduced. We thus demonstrate a prototypical system in which the photon-induced nuclear motion (proton transfer) is directly coupled with solvent polarization and the corresponding mechanism is reminiscent of that applied in ail electron transfer process.