The energetically unfavorable termination of the hydrogen-bonded network of water molecules at the air/water interface causes molecular rearrangement to minimize the free energy. The long-standing question is how water minimizes the surface free energy. The combination of advanced, surface-specific nonlinear spectroscopy and theoretical simulation provides new insights. The complex χ(2) spectra of isotopically diluted water surfaces obtained by heterodyne-detected sum frequency generation spectroscopy and molecular dynamics simulation show excellent agreement, assuring the validity of the microscopic picture given in the simulation. The present study indicates that there is no ice-like structure at the surface-in other words, there is no increase of tetrahedrally coordinated structure compared to the bulk-but that there are water pairs interacting with a strong hydrogen bond at the outermost surface. Intuitively, this can be considered a consequence of the lack of a hydrogen bond toward the upper gas phase, enhancing the lateral interaction at the boundary. This study also confirms that the major source of the isotope effect on the water χ(2) spectra is the intramolecular anharmonic coupling, i.e., Fermi resonance.