Complex chi(2) spectra of air/water interfaces in the presence of charged surfactants were measured by heterodyne-detected broadband vibrational sum frequency generation spectroscopy for the first time. In contrast to the neat water surface, the signs of chi(2) for two broad OH bands are the same in the presence of the charged surfactants. The obtained chi(2) spectra clearly showed flip-flop of the interfacial water molecules which is induced by the opposite charge of the head group of the surfactants. With the sign of beta(2) theoretically obtained, the absolute orientation, i.e., up/down orientation, of water molecules at the charged aqueous surfaces was uniquely determined by the relation between the sign of chi(2) and the molecular orientation angle. Water molecules orient with their hydrogen up at the negatively charged aqueous interface whereas their oxygen up at the positively charged aqueous interface.