We have developed a simple technique to measure the phase of the weak surface optical second-harmonic response to excitation with femtosecond laser pulses that uses the principle of spectral interference. This approach is necessary for the study of surfaces under ͑ultrahigh͒ vacuum conditions, where the conventional method fails due to the dispersion in optical windows. As a demonstration, we have applied the technique to clean Ni͑110͒ in UHV and to a Rh/Co/Cu multilayer in air. We have determined the phase with an accuracy of 5°which is comparable to the conventional method. ͓S0163-1829͑98͒50548-6͔Optical second-harmonic generation ͑SHG͒ has attracted significant attention due to its high sensitivity to the electronic, magnetic, geometric, etc., structure of surfaces and interfaces. [1][2][3][4] The surface sensitivity stems from the fact that SHG is dipole forbidden in the bulk of centrosymmetric media but is allowed at interfaces where the centrosymmetry is lifted. In surface SHG experiments only the intensity of the generated harmonic light is usually measured. The phase of the second-harmonic ͑SH͒ light does, however, often contain valuable information for a correct interpretation of the experimental data. Furthermore, phase-sensitive measurements are especially useful in surface-specific second-harmonic generation where the response mainly originates from a thin surface region so that the optical phase is directly related to the phase of the components of the surface second-order susceptibility (2),S . As an example the phase may give direct information about molecular orientation on surfaces 5 and in liquid crystals. 6 In magnetization-induced second-harmonic generation ͑MSHG͒, phase information is needed to evaluate the relative size of the odd ͑magnetic͒ and even ͑nonmag-netic͒ tensor elements. [7][8][9] The phase of the SH response can be determined by employing an interference technique originally introduced by Chang et al. 10 This method, however, is not compatible with, for example, ultrahigh vacuum ͑UHV͒ experiments when femtosecond lasers are used. The reason is the dispersion of the optical windows (⌬n glass ϳ10 Ϫ2 ), causing a too large time delay ( ϳ1 ps͒ between the fundamental and SH pulses that destroys the interference. For studying clean surfaces, UHV conditions are nevertheless unavoidable, leading to a demand for an alternative approach. In this paper we show that by making use of spectral interferometry, 11,12 phase-sensitive measurements in UHV are readily accessible. We believe our technique to be easy, accurate, and reliable.When a SH (2 ) and a fundamental ( ) pulse ͑described by their amplitudes E SH and E f ) propagate through air, the relative phase ⌽ between E SH and E f 2 gradually changes,where ⌬n air ϭn(2 )Ϫn( )ϳ10 Ϫ5 is the dispersion of the ambient air, d is the distance the two pulses travel through air, and is the wavelength of the fundamental pulse. By using an additional SHG source ͑reference͒ at position d in the path of the beam, interference can be observed in the d...