Apparent molar volumes V 2,ϕ , apparent molar isentropic compressibilities K S , 2,ϕ and viscosity B-coefficients have been determined for L-ascorbic acid, nicotinic acid, thiamine hydrochloride and pyridoxine hydrochloride in water at temperatures (288.15–318.15)K from density, speed of sound and viscosity measurements, respectively. Partial molar volumes V2o and partial molar isentropic compressibilities KS,2o at infinite dilution, and viscosity B-coefficients have been calculated from the corresponding data. The partial molar expansibilities VEo (VEo=(∂V2o/∂T)P), second order derivative (∂2V2o/∂T2)P and solvation number (S n ) have been calculated. Both volumetric and viscometric studies indicate that nicotinic acid acts as structure promoter where as other vitamins act as structure destroyer. The transition state theory has been used to calculate the activation free energy for viscous flow.