Time-resolved second harmonic generation spectroscopy of a solvatochromic dye coumarin 314 was used to investigate how the solvation dynamics at the air/water interface are affected by lipid surfactants with anionic carboxylate and sulfate headgroups. The surfactants were chosen to mimic common functional groups and the negative charge of biological aqueous interfaces such as cell membranes and folded proteins. The diffusive component of the solvation response, associated with rearrangement of the water hydrogen bond network, exhibits a biexponential decay. The two time scales change as a function of the surface charge density, compared to the bare air/water interface solvation dynamics, tau(1) = 250 +/- 50 fs and tau(2) = 2.0 +/- 0.4 ps, which are similar to the bulk water response, tau(1) = 130-250 fs and tau(2) = 0.6-1.2 ps. The faster tau(1) component is unaffected at low to intermediate sulfate surface coverage (270 +/- 50 fs at 500 Angstrom(2)/molecule and 225 +/-25 fs at 250 Angstrom(2)/molecule) but becomes slower at high surface coverage (100 Angstrom(2)/molecule), 600 +/- 70 fs. The slower tau(2) component changes even at the lowest coverage: tau(2) = 4.4 +/- 0.9 ps at 500 Angstrom(2)/molecule; 5.2 +/-0.7 ps at 250 Angstrom(2)/molecule; and 5.4 +/- 1.1 ps at 100 Angstrom(2)/molecule. Different behavior of the two solvation components indicates that they represent different water motions. The solvation dynamics compared with the structure-sensitive surface vibrational spectroscopy of the same interface [Gragson, D. E.; McCarty, B. M.; Richmond, G. L. J. Am. Chem. Soc. 1997, 119, 6144. Gragson, D. E.; Richmond, G. L. J. Am. Chem. Soc. 1998, 120, 366.] show a similar dependence on surfactant coverage. For the first time, to our knowledge, a relation is made between a dynamical relaxation mode, the slower diffusive solvation time scale tau(2), and a spectral feature, in this case the strongly hydrogen-bonded water structures induced by the negative surface charge. The carboxylate and sulfate surfactants induce similar dynamics, suggesting that the solvation is not sensitive to the chemical composition of the headgroup but rather to the total negative surface charge density.