Carbon tetrachloride dissociatively adsorbs on the Ga-rich (4x2) reconstruction of GaAs (001) at 200 degrees C. Upon heating to 440 degrees C, the chlorine desorbs as GaCl, which etches the surface. Scanning tunneling micrographs reveal that this reaction transforms the (4x2) into a Ga-rich (3x2) structure that is interlaced with As-rich (2x4) phases. The (3x2) is well ordered, while the (2x4) phases exhibit a high degree of disorder. This work establishes the surface reaction pathway for carbon doping of GaAs with CCl4. (C) 1998 American Institute of Physics.