We have studied the soft laser sputtering of (100)GaAs with 337 nm photons, starting from the threshold for particle emission (a few tens of mJ/cm2) to some 300 mJ/cm2fluences. Atoms and molecules sputtered from the irradiated surface are detected, their relative number measured, and their time of flight determined using laser resonant ionization mass spectrometry. The surface after laser irradiation is examined by scanning electron microscopy and electron microprobe analysis.One observes a significant preferential emission of arsenic in the form of As2. This leads to the formation of perturbed Ga‐rich surface structure which appears even at low fluence and after a few tens of laser shots on the same spot. This initial transformation seems to determine the further evolution of the irradiated surface. First, Ga atoms aggregate to form Ga islands on the surface; after a sufficient number of shots, micrometric structures are produced which finally behave as pure Ga metal. This evolution of the surface state after multipulse irradiation appears practically the same for low and medium laser fluences, the only difference being in the number of shots required to obtain the same microscopic structure. The velocity distribution of Ga atoms and As2molecules is well fitted by half‐space Maxwellian distributions. The kinetic temperatures are in broad agreement with the results obtained from a model of laser heating of the surface. The gross features of the experimental results can be interpreted from the particular thermodynamics properties of GaAs which exhibits very large As2pressure above the solid as soon as the temperature exceeds 950 K. After a few laser shots, corresponding to particle emission from defect sites, the thermodynamics of GaAs appears to govern the further evolution of the laser‐sputtered surface. Two sputtering regimes are evidenced: In the low‐fluence regime (from threshold to 90 mJ/cm2) sputtering appears to be dominated by surface defect emission, whereas for higher fluences emission is more characteristic of thermal process accompanied by preferential sputtering of arsenide. According to these experimental results, a simple analytical model was developed which relates the quantitative surface to the quantitative sputtered cloud compositions. ©1995 American Institute of Physics.