We investigated the use of multispectral thermal imagery to retrieve land surface emissivity and temperature. Conversely to concurrent methods, the temperature emissivity separation (TES) method simply requires single overpass without any ancillary information. This is possible since TES makes use of an empirical relationship that estimates the minimum emissivity ε-min from the emissivity spectral contrast captured over several channels, so-called maximum-minimum difference (MMD). In previous studies, the ε-min - MMD empirical relationship of TES was calibrated and validated for various sensor spectral configurations, where the proposed calibrations involved single or linearly mixed spectra of emissivity at the leaf or soil level. However, cavity effect should be taken into account at the vegetation canopy level, to avoid an underestimation of emissivity, especially for intermediate vegetation conditions between bare soil and full vegetation cover. The current study aimed to evaluate the performances of the TES method when applied to vegetation canopies with cavity effect. We used the SAIL-Thermique model to simulate a library of emissivity spectra for a wide range of soil and plant conditions, and we addressed the spectral configurations of recent and forthcoming sensors. We obtained good results for calibration and validation over the simulated library, except for full cover canopies because of the TES gray body problem. Consistent with previous studies, the calibration/validation results were better with more channels that capture emissivity spectral contrast more efficiently. Our TES calibrations provided larger ε-min values as compared to former studies, especially for intermediate vegetation cover. We explained this trend by the simulated spectral library that involved numerous vegetation canopies with cavity effect, thereby shifting up the ε-min - MMD empirical relationship. Consequently, our TES calibration provided larger (respectively lower) estimates of emissivity (respectively radiometric temperature) that were likely to be more realistic as compared to previous calibrations. Finally, SAIL-Thermique simulations permitted to show that increasing Leaf Area Index induced a displacement of the (ε-min, MMD) pairs along the empirical relationship. This was consistent with the TES underlying assumption, where any change in ε-min induces changes in MMD since ε-max is bounded on [0.98–1]. Further investigations should focus on validating the outcomes of the current study against ground-based measurements, and on assessing TES performances when accounting for instrumental and atmospheric perturbations.