In the present study of proton-coupled electron transfer (PCET) reactions, the excited-state of a fac-[(CO)3ReI(bpy)(4,4′-bpy)]+ (bpy = 2,2′-bipyridine and 4,4′-bpy = 4,4′-bipyridine) complex was reductively quenched by a series of phenols. A variation of substituents on the phenols substantially alters their pKa and E° values and provides an opportunity to study photoinduced PCET as a function of their redox properties. Analyses of absorption spectral changes indicate that the phenols form a weak hydrogen bond with the pyridinic nitrogen of the 4,4′-bpy ligand in the ground-state, and ground-state association constant (KA) values were determined. This H-bonded adduct quenches the excited Re complex by PCET from the phenol, to form the reduced and protonated Re complex. The KA values obtained aid quantitative evaluation of the rate constant for the PCET reaction in the H-bonded adduct. Thus, photophysical studies and mechanistic analysis indicate that the reaction occurs via a concerted mechanistic pathway, for the unsubstituted phenol and phenols with electron-withdrawing substituents. Furthermore, the magnitude of the quenching varies systematically with the proton-coupled potentials of the phenols and not their hydrogen-bonding strength (as reflected in KA). This study is one of the first detailed analyses of intermolecular H-bonding between a self-assembling metal complex and a series of substituted phenols in an effort to study their relationship with the kinetic parameters in a photoinduced CPET reaction. © 2017 American Chemical Society.