The photothermally induced nanoscale dynamics of rapid melting and resolidification of a thin layer of molecular material surrounding a nanoparticle is examined in real time by an all-optical approach. The method employs pulsed periodic modulation of the medium’s dielectric constant through absorption of a low-duty-cycle laser pulse train by a single nanoparticle that acts as a localized heating source. Interpretation of experimental data, including inference of a phase change and of the liquid/solid interface dynamics, is obtained by comparing experimental data with results from coupled optical–thermal numerical simulations. The combined experimental/computational workflow presented in this proof-of-principle study will enable future explorations of material parameters at nanoscale, which are often different from their bulk values and in many cases difficult to infer from macroscopic measurements. -  Copyright © 2022 American Chemical Society