Thick smoothly graded AlxGa1−xAs layers (50–100 µm) are used in light-emitting diode structures and also for creation of high-power photovoltaic converters with side-input of laser radiation. To achieve the required thickness of the AlxGa1−xAs layer the high temperature LPE growth technique is required. However high epitaxial temperature increases the unintentional doping level. Epitaxy from mixed Ga–Bi melts was investigated as a way to solve this problem. It was found that for growing relatively thick AlxGa1−xAs layers, it is expedient to use Ga–Bi melts with 20 at% or less bismuth content. SIMS and Hall characterization of AlxGa1−xAs layers revealed that the growth of AlxGa1−xAs from mixed Ga-Bi melts reduces the background doping level (including carbon) and influences the native defect formation keeping the n-type conductivity. This effect is explained by the changes of the group III and V elements concentrations in the melt as well as Bi incorporation in the lattice.