The FLuorescence EXplorer (FLEX) satellite mission, selected as ESA's 8th Earth Explorer, has been designed for the measurement of sun-induced fluorescence (F) spectra emitted by plants. This will be accomplished through a multi-sensor approach by placing it in a common orbit in tandem with the Sentinel-3 (S3) mission, which will have two optical sensors on board, OLCI (Ocean and Land Colour Instrument) and SLSTR (Sea and Land Surface Temperature Radiometer) to complement FLEX. These S3 instruments will be used in combination with the imaging spectrometers on board FLEX to provide data useful for atmospheric correction of FLEX data. However, a fully synergetic approach, i.e. by exploiting the spectral and directional information from all tandem mission instruments together, is an attractive alternative which is explored in this paper. By employing all combined top-of-atmosphere (TOA) spectral radiance data, one can (i) characterize the relevant optical properties of the atmosphere, (ii) retrieve biophysical canopy properties including the associated reflectance anisotropy, and (iii) retrieve a more accurate and consistent canopy F.Regarding retrieval methods, Fraunhofer Line Depth (FLD) and Spectral Fitting (SF) are well-known techniques applied to hyperspectral data. Both methods depend on a high spectral resolution and assume a Lambertian (isotropic) canopy reflectance. However, most vegetation canopies are non-Lambertian. This implies that, in particular when ignoring the anisotropic surface reflection, substantial retrieval errors can occur due to the interaction between atmospheric absorption bands and surface reflectance anisotropy. In this paper, a novel method based on spectral radiative transfer (RT) modeling is proposed, in which coupled RT models are used to simulate TOA radiance spectra. These are then matched with ‘measured’ spectra in order to retrieve surface fluorescence, along with a suite of biophysical parameters, by model inversion through optimization. By applying coupled RT models of the soil-leaf-canopy and the surface-atmosphere systems, TOA radiance spectra can be simulated for all optical sensors of this tandem mission. In this way, complex effects due to surface reflectance anisotropy and the spectral sampling by the various instruments, which are difficult to compensate for in the end products, are properly taken into account by their incorporation in the forward modeling. Next, by model inversion of TOA radiance data via optimization, the most accurate F retrievals can be achieved in a consistent manner, along with important canopy level biophysical parameters that may help interpret the F spectrum, such as chlorophyll content and leaf area index (LAI). The potential of this approach has been explored in a numerical experiment, and the results are presented in this paper. We find that, with the assumed well-characterized and plausible FLEX/S3 instrument performances, the simultaneous retrieval of biophysical canopy parameters and F spectra would be possible with a remarkable accuracy, provided the correct atmospheric characterization is available.