It has recently been shown that a 1000Å cap layer of molecular beam epitaxial (MBE) GaAs grown at 200°C passivates the surface of a GaAs active layer (n≃2×1017cm−3) in the sense of reducing the free–carrier depletion which arises from surface acceptor states. The same phenomenon holds for active-layer concentrations up to 7×1018cm−3, for caps as thin as 14Å, and for either As2 or As4 anion species. In an attempt to understand these effects, we have applied photoreflectance (PR) and x–ray photoelectron spectroscopy (XPS). In general, the PR shows contributions from the surface, cap/active–layer interface, and active–layer/buffer–layer interface, because each of these regions can have a different electric field. In fact the various field strengths can be determined from Franz–Keldysh oscillations (FKO), and good agreement with Hall–effect measurements is usually found. However, for 200°C material, no PR is seen, suggesting that there is no surface charge (no surface acceptor states below the Fermi level) or at least no surface–charge modulation by the light. The XPS data, which arise only from the near–surface (∼30Å) region, show that the binding energies in the capped samples are increased (i.e., surface Fermi pinning energy decreased) by 0.2 eV with respect to those in the uncapped samples. These data are discussed in relation to a passivation model.