Vegetation water content retrieval using passive remote sensing techniques in the 0.4–2.5μm region (reflection of solar radiation) and the 8–14μm region (emission of thermal radiation) has given rise to an abundant literature. The wavelength range in between, where the main water absorption bands are located, has surprisingly received very little attention because of the complexity of the radiometric signal that mixes both reflected and emitted fluxes. Nevertheless, it is now covered by the latest generation of passive optical sensors (e.g. SEBASS, AHS). This work aims at modeling leaf spectral reflectance and transmittance in the infrared, particularly between 3μm and 5μm, to improve the retrieval of vegetation water content using hyperspectral data. Two unique datasets containing 32 leaf samples each were acquired in 2008 at the USGS National Center, Reston (VA, USA) and the ONERA Research Center, Toulouse (France). Reflectance and transmittance were recorded using laboratory spectrometers in the spectral region from 0.4μm to 14μm, and the leaf water and dry matter contents were determined. It turns out that these spectra are strongly linked to water content up to 5.7μm. This dependence is much weaker further into the infrared, where spectral features seem to be mainly associated with the biochemical composition of the leaf surface. The measurements show that leaves transmit light in this wavelength domain and that the transmittance of dry samples can reach 0.35 of incoming light around 5μm, and 0.05 around 11μm. This work extends the PROSPECT leaf optical properties model by taking into account the high absorption levels of leaf constituents (by the insertion of the complex Fresnel coefficients) and surface phenomena (by the addition of a top layer). The new model, PROSPECT-VISIR (VISible to InfraRed), simulates leaf reflectance and transmittance between 0.4μm and 5.7μm (at 1nm spectral resolution) with a root mean square error (RMSE) of 0.017 and 0.018, respectively. Model inversion also allows the prediction of water (RMSE=0.0011g/cm²) and dry matter (RMSE=0.0013g/cm²) contents.