There is a large number of technologically important semiconducting optoelectronic materials with narrow band-gaps in the "finger-print" region of the infra-red (IR) spectrum. However, in many instances their band-structures have not been very well characterised, making it difficult to engineer their properties. Part of the reason is that the key non-destructive optical characterisation tool, modulation spectroscopy, becomes increasingly difficult as one attempts to look further out into the IR. To date, conventional diffraction-grating-based modulation spectroscopy has been applied predominantly below ~4 µm. We have developed a new photo-modulation system, based on a Fourier transform spectrometer, that permits such measurements out to much longer wavelengths. We discuss the advantages and technical difficulties of implementing such a system, and give the results obtained so far for narrower-gap materials, including bulk-like GaSb, InAs and InSb, comparing these with what can be obtained with conventional modulation spectroscopy arrangements. We apply our new technique to measure the bandgap in dilute-N InSbN, achieving what we believe are the first modulation spectroscopy measurements in the mid-IR beyond ~6 µm. optical property (e.g. transmittance, or more usually, reflectance R) is probed by a spectrally-resolved source while its dielectric function is being simultaneously externally modulated at frequency ν mod . In the case of reflectance, the modulated (AC) component, ∆R, is usually detected with sensitive lock-in techniques, yielding sharp, differential-like oscillatory spectra. In electro-modulated reflectance an applied AC electric field modulates any high resistance region in the structure directly. The most widely used version, photo-modulated reflectance (PR) [1] uses a chopped laser pump beam with photon energy above the band-gap. When the laser is on, generated carriers are captured by traps, thus reducing the inbuilt/surface electric fields. When the laser is off, the trap population, and hence field, are restored [2]. This mechanism modulates the Stark shift of, say, the quantum well (QW) levels which modulates the dielectric function, and thus the relative reflectivity, ∆R/R. Uninteresting broad background or systemresponse features in R are removed. At room temperature PR can give equivalent energy resolution to that obtained by PL and PLE at liquid helium temperatures, and probes a far wider range of critical point transition energies, yielding all these in a single spectrum, highlighting not only ground-state but also many higher-order critical point interband optical transitions, from which transition energies, and thus band-structure, can be accurately obtained. Unlike PLE, PR can be carried out using a white light blackbody radiator source (e.g. tungsten filament lamp), a simple diffraction grating spectrometer (e.g. 0.5 metre), and a small mechanically-chopped laser (such as a 3 mW, 633 nm HeNe) and so is applicable over a fairly wide wavelength range using the same equipment.Thus, modula...