Gadolinium (Gd) is a suitable material for neutron conversion because of its superior neutron absorption cross-section. However, the principal secondary particles that generate electron-hole pairs in a semiconductor detector after Gd neutron capture are low-energy internal conversion (IC) electrons. We measured the IC electron spectrum due to Gd neutron capture by using a thermal neutron beam and a digitizer-based multidetector spectroscopy. We also discussed the effective use of the IC electrons in the context of a twin-detector design and the associated gamma-ray rejection issues. Extensive simulations of the spectra of IC electrons and gamma rays agreed well with the experimental results; both types of results support the feasibility of the proposed n–γ separation method.