Using pump-probe electron microscopy techniques, the dewetting of thin nickel films exposed to a pulsed nanosecond laser was monitored at tens of nanometers spatial and nanosecond time scales to provide insight into the liquid-phase assembly dynamics. Thickness-dependent and correlated time and length scales indicate that a spinodal instability drives the assembly process. Measured lifetimes of the liquid metal are consistent with finite-difference simulations of the laser-irradiated film and are consistent with estimated and observed spinodal time scales. These results can be used to design improved synthesis and assembly routes toward achieving advanced functional nanomaterials and devices.