High-quality AlGaAs/GaAs heterostructures have been grown on on-axis (111)B GaAs substrates using molecular-beam epitaxy to study the effect of As4 pressure on the material qualities. It was found that the electrical and structural properties were strongly dependent on the As4 pressure. The quality of the heterostructure was investigated by Hall effect, atomic force microscopy, and high-resolution x-ray diffraction measurements. The electron Hall mobility dropped from 7200 and 90 000 cm2/V s to 930 and 1340 cm2/V s at room temperature and 77 K, respectively, as As4 pressure was increased from 4.9×10−6 to 1.1×10−7 Torr. The same trend was observed at the root-mean-square roughness of the AlGaAs/GaAs heterostructures measured by atomic force microscopy, and the intensity and full width at half-maximum of the x-ray diffraction curve.