Many plant species have dorsiventral leaves that have significant differences in optical properties from one side to the other. Several studies have revealed that ignoring this asymmetry induces significant errors in plant canopy reflectance, and current leaf models simulating leaf dorsiventrality are limited to the 0.4–2.5 μm wavelength range. This article, partly based on two recently collected datasets in the 2.5–14 μm wavelength range, demonstrates that ignoring leaf dorsiventrality induces significant errors in brightness temperature and effective emissivity at the canopy scale. The PROLIB model, which inherits from the PROSPECT-VISIR and LIBERTY models, is the first radiative transfer model to simulate the reflectance and transmittance of both leaf sides from 0.4 to 5.7 μm. The palisade and spongy mesophylls are represented as plate and sphere layers, respectively, to account for the structural asymmetry of leaf cells. The sieve effect that explains the differences in transmittance between the adaxial and abaxial sides of the leaf is successfully incorporated into PROLIB. Evaluation of the model on several leaf datasets shows that: (1) It reproduces well the adaxial and abaxial optical properties of the leaves, with a root mean square error (RMSE) of 0.0109 for reflectance and transmittance. (2) It can be inversed to retrieve leaf traits, with RMSE values for leaf chlorophyll, carotenoid, anthocyanin, water, and dry matter content of 5.519 μg/cm2, 2.344 μg/cm2, 4.219 μg/cm2, 0.0022 g/cm2, and 0.0017 g/cm2, respectively (corresponding normalized RMSE values of 22.0%, 34.0%, 49.4%, 19.6%, and 24.7%). However, better and more complete leaf datasets are needed for leaf dorsiventrality analysis and model calibration.