Three‐inch, semi‐insulating (SI) GaAs, grown by the vertical gradient freeze (VGF) technique, has been studied by IR absorption, temperature‐dependent dark current and Hall‐effect, thermally stimulated current (TSC), and photoinduced current transient spectroscopy and has been compared with undoped, SI GaAs, both As‐rich and Ga‐rich, grown by the high‐pressure liquid‐encapsulated Czochralski method. The results clearly indicate that (1) the VGF GaAs contains less EL2, which suggests a less As‐rich crystal stoichiometry; (2) in some VGF samples activation energies of 0.43 or 0.46 eV are deduced from temperature‐dependent carrier concentration or resistivity measurements, respectively, and (3) VGF samples often show a thermal quenching behavior in the TSC peak T5. There is evidence to suggest that the 0.43 eV center is related to VAs, and T5 to VGa.