Excited states in the nucleus 133Sn, with one neutron outside the doubly-magic 132Sn core, were populated following one-neutron knockout from a 134Sn beam on a carbon target at relativistic energies at the Radioactive Isotope Beam Factory at RIKEN. Besides the γ rays emitted in the decay of the known neutron single-particle states in 133Sn additional γ strength in the energy range 3.5-5.5 MeV was observed for the first time. Since the neutron-separation energy of 133Sn is low, Sn=2.402(4) MeV, this observation provides direct evidence for the radiative decay of neutronunbound states in this nucleus. The ability of electromagnetic decay to compete successfully with neutron emission at energies as high as 3 MeV above threshold is attributed to a mismatch between the wave functions of the initial and final states in the latter case. These findings suggest that in the region south-east of 132Sn nuclear structure effects may play a significant role in the neutron vs. γ competition in the decay of unbound states. As a consequence, the common neglect of such effects in the evaluation of the neutron-emission probabilities in calculations of global β-decay properties for astrophysical simulations may have to be reconsidered.