Nonintentionally doped AlxGa1−xAs layers with 0.38 x 0.84 were grown on (100) GaAs substrates by liquid phase epitaxy (LPE) under near-equilibrium conditions. The crystalline quality of the samples was studied by photoluminescence at 2 K and room temperature Raman spectroscopy. The peculiar behavior in the photoluminescence intensities of the indirect bound exciton line and the donor–acceptor pair transition is explained from the evolution of the silicon donor binding energy according to the aluminum composition. It was also possible to observe the excitonic transition corresponding to the AlxGa1−xAs/GaAs interface, despite the disorder and other factors which are normally involved when growing high-aluminum-content layers by this technique. Furthermore, Raman measurements show the quadratic variations of longitudinal optical phonon frequencies with aluminum concentration in good agreement with previous experimental results. In this work we show that high quality indirect-gap AlxGa1−xAs samples can be grown by LPE under near-equilibrium conditions.