High-frequency surface-wave techniques are widely used to estimate S-wave velocity of near-surface materials. Surface-wave methods based on inversions of dispersion curves are only suitable to laterally homogeneous or smoothly laterally varying heterogeneous earth models due to the layered-model assumption during calculation of dispersion curves. Waveform inversion directly fits the waveform of observed data, and it can be applied to any kinds of earth models. We have used the Love-wave waveform inversion in the time domain to estimate near-surface S-wave velocity. We used the finite-difference method as the forward modeling method. The source effect was removed by the deconvolution technique, which made our method independent of the source wavelet. We defined the difference between the deconvolved observed and calculated waveform as the misfit function. We divided the model into different sizes of blocks depending on the resolution of the Love waves, and we updated the S-wave velocity of each block via a conjugate gradient algorithm. We used two synthetic models to test the effectiveness of our method. A real-world case verified the validity of our method.