The organization of nanowires on surfaces remains a major obstacle toward their large-scale integration into functional devices. Surface-material interactions have been used, with different materials and substrates, to guide horizontal nanowires during their growth into well-organized assemblies, but the only guided nanowire heterostructures reported so far are axial and not radial. Here we demonstrate the guided growth of horizontal core-shell nanowires, specifically of ZnSe@ZnTe, with control over their crystal phase and crystallographic orientations. We exploit the directional control of the guided growth for the parallel production of multiple radial p-n heterojunctions, and probe their optoelectronic properties. The devices exhibit a rectifying behavior with photovoltaic characteristics upon illumination. Guided nanowire heterostructures pave the way to the bottom-up assembly of complex semiconductor structures with controlled electronic and optoelectronic properties.