The band bending on GaAs(001) surfaces prepared by molecular beam epitaxy (MBE) have been studied forn‐ andp‐type materials. Surfaces withc(4×4),c(2×8), and (4×6) reconstruction ranging from As to Ga rich have been investigated. The surface symmetry was determined by reflection high energy electron diffraction (RHEED) and the position of the valence band maximum relative to the Fermi level was measured using angle resolved UV photoelectron spectroscopy (ARUPS) at normal emission. The position of the Fermi level relative to the valence band maximum was found to be ∼0.7 eV forn‐type and ∼0.5 eV forp‐type material, with a slightly increasing trend in going from Ga‐ to As‐rich surfaces. For the (4×6) reconstructedn‐type samples the growth termination method was found to have a significant influence on the band bending. The results obtained here are in very good agreement with previous measurements of the Al–GaAs(001) Schottky barrier height indicating that the electronic properties of this junction are determined by the properties of the semiconductor.