Time-resolved photoacoustic calorimetry (TR-PAC) and quantum chemistry calculations were used to investigate the energetics of sulfur−hydrogen bonds in thiophenol and four para-substituted thiophenols, 4-XC₆H₄SH (X = CH₃, OCH₃, Cl, and CF₃). The result obtained for the PhS−H gas-phase bond dissociation enthalpy, derived from the PAC experimental results in solution, is 349.4 ± 4.5 kJ mol^-1. This value is significantly higher than recent literature values but agrees with a value suggested some 20 years ago in a widely used review. The PAC result also concurs with the value computed at a high theory level, G3(MP2), 346.8 kJ mol^-1. The data obtained for the substituted thiophenols support the idea that substituent effects are less pronounced on the S−H bond dissociation enthalpy than on the O−H bond dissociation enthalpy of the corresponding phenols.