The dynamics of explosive boiling of a 2-propanol layer of variable thickness on a Si substrate heated by a nanosecond KrF excimer laser was studied using a contact photoacoustic technique. The transition from acoustic generation at a free Si boundary to that at a rigid alcohol/Si boundary accompanied by a sharp increase of acoustic generation efficiency was found above a laser fluence threshold of 0.17 J/cm2 and a liquid layer thickness greater than 0.25 μm due to subnanosecond near-critical explosive boiling of the superheated liquid layer near the hot absorbing Si substrate. The gradual increase of the photoacoustic response of the superheated alcohol with increasing thickness of the liquid film at fluences above the explosive boiling threshold was attributed to a diffraction effect due to the fluence- and time-dependent increase of the area undergoing explosive boiling. A model describing photoacoustic generation and subsequent lift-off of the entire liquid layer in this experimental “thin transparent liquid layer/solid absorbing substrate” geometry under near-critical explosive boiling conditions has been proposed.