The orientation of the isopropyl group at the liquid/vapor interface in 2-propanol/water binary mixtures was studied by vibrational sum frequency spectroscopy. The CH3 stretch modes of the two methyl groups were used to determine the molecule's orientation by employing a novel united atom approach to model the (CH3)(2)X moiety. For this purpose, the changes in the molecular susceptibility of the isopropyl group stretches were derived in the laboratory frame as a function of the tilt and twist angles. The results indicated that the methyl groups lay down on the surface at low alcohol mole fraction and gradually twisted with increasing mole fraction. At the azeotrope, x(iso) = 0.68, one of the methyl groups aligned approximately parallel to the surface normal, whereas the other was nearly parallel with the liquid/vapor interface. When the mole fraction of 2-propanol was higher than 0.68, the orientation of 2-propanol remained almost constant. The change in the alcohol's orientation with 2-propanol mole traction closely tracked changes in its bulk activity coefficient. Such results lead to a picture in which the surface structure and bulk properties of the system are closely linked.