We propose an arsenic-capping/decapping method, allowing the growth of an epitaxial shell around the GaAs nanowire (NW) core which is exposed to an ambient atmosphere, and without the introduction of impurities. Self-catalyzed GaAs NW arrays were firstly grown on Si(111) substrates by solid-source molecular beam epitaxy. Aiming for protecting the active surface of the GaAs NW core, the arsenic-capping/decapping method has been applied. To validate the effect of this method, different core/shell NWs have been fabricated. Analyses highlight the benefit of the As capping–decapping method for further epitaxial shell growth: an epitaxial shell with a smooth surface is achieved in the case of As-capped–decapped GaAs NWs, comparable to the in situ grown GaAs/AlGaAs NWs. This As capping method opens a way for the epitaxial growth of heterogeneous material shells such as functional oxides using different reactors.