The extension of time-resolved X-ray diffraction to the subpicosecond domain is an important challenge, as the nature of chemical reactions and phase transitions is determined by atomic motions on these timescales. An ultimate goal is to study the structure of transient states with a time resolution shorter than the typical period of vibration along a reaction coordinate (around 100 fs). Biological precesses that can be initiated optically have been studied extensively by ultrafast infrared, visible and ultraviolet spectroscopy(1). But these techniques probe only electronic states, whereas time-resolved crystallography should be able to directly monitor atomic positions. Here we show that changes in the X-ray diffraction pattern from an organic film heated by a laser pulse can be monitored on a timescale of less than a picosecond. We have studied the response of a Langmuir-Blodgett multilayer film of cadmium arachidate to laser hearing by observing changes in the intensity of one Bragg peak for different delays between the perturbing optical pulse and the Xray probe pulse. ii strong decrease in intensity is seen within a picosecond of heating, resulting from disorder introduced to the layers of cadmium atoms before thermal expansion of the film (which ultimately leads to its destruction) has time to occur.