The electronic excited-state solvation dynamics of coumarin 314 (C314) adsorbed at the air/water interface was investigated by femtosecond time-resolved second-harmonic generation (TRSHG). The second-harmonic spectrum of C314 at the air/water interface was determined using a tunable optical parametric generator, giving a spectral peak at 419 +/- 3 nm. The solvatochromic shift is in good agreement with the recently proposed interfacial polarity scale, which predicts that the empirical polarity parameter of the interface is the arithmetic mean of the two bulk phases. The time-resolved second-harmonic response to the excited-state solvation was measured at two fundamental wavelengths (840 and 900 nm) and with two pump polarizations (S and P). The results indicate that the static spectral peaks of the S- and P-pumped distributions are offset similar to5 nm, while the dynamic interfacial solvation proceeds with two time constants, tau (1) = similar to 200 fs and tau (2) = 1.2 ps, which are independent of C314 interfacial orientation. The slight blue shift of the C314 molecules closer to the normal incidence indicates that the electronic spectra of species at the air/water interface is inhomogeneously broadened by orientation, an effect which had not been observed previously. This can be described by a static solvation that depends on the orientation of the molecule's dipole moment at the interface. The dynamic solvation times are consistent with bulk experiment, as well as theory, which indicates that the air/water relaxation times, which are controlled by water/water interactions, should not be different from the bulk values.