The growth of GaAs thin films from the excimer laser photolysis of trimethylarsine (TMAs) and trimethylgallium (TMGa) at 193 nm is reported. Scanning electron microscopy (SEM), electron channeling, Rutherford backscattering spectroscopy (RBS), transmission electron microscopy (TEM), and Auger electron spectroscopy (AES) were used to characterize the films. Incident laser fluences on the surface of 0.096–0.115 J/cm2 lead to carbon desorption, adatom mobility, transient annealing and hence epitaxial growth. However, TEM micrographs also revealed the growth of GaAs twins along the <110> direction in a novel periodic fashion, with a spacing equal to that of the ArF excimer laser wavelength (193 nm). Time-resolved mass spectrometry, used to determine gas-phase photolysis products created during the deposition process, showed that AsCH3 and higher gallium-alkyls are significant products which transport As and Ga to the surface.