Phase transformations at the Si–H2O interface, induced by nanosecond pulsed laser irradiation, were studied in real time. Si samples were irradiated using a 4 ns pulse from a Q-switched frequency-doubled Nd:YAG laser while immersed in the transparent liquid. Using time-resolved conductivity and reflectivity techniques, in combination with modeling of optical parameters and heat flow, transient processes in the Si, the H2O, and at the interface have been unraveled. In the liquid, local rapid heating occurs as a result of heat flow across the interface, and formation of a low-density steam phase occurs on a nanosecond timescale. Expansion of this phase is followed by a collapse after 200 ns. These rapid phase transformations in the water initiate a shock wave with a pressure of 0.4± 0.3 kbar. Transient phase transformations and the heat flow into the water during the laser pulse influence the energy coupling into the sample, resulting in an effective laser pulse shortening. The pulse shortening and the additional heat flow into the water during solidification result in a 30% enhancement of the solidification velocity for 270 nm deep melts. Cross-section transmission electron microscopy data reveal that the Si surface is planar after irradiation and is inert to chemical reactions during irradiation. Recent experiments described in the literature concerning pulsed-laser induced synthesis at the solid-liquid interface are reviewed and discussed in the context of the fundamental phenomena presently observed.