Résumé : S stars are cool stars of temperatures similar to those of M giants, but their atmospheres are enriched in carbon and s-process elements because of either extrinsic pollution by a binary companion or intrinsic nucleosynthesis and dredge-up on the thermally-pulsing AGB. Despite numerous attempts to link phenomenological spectral classification criteria to physical parameters (T eff, gravity, C/O, [s/Fe], [Fe/H]), the parameter space of S stars is poorly known and this has prevented accurate abundance analysis of S stars until now. Here we present a large grid of S-star model atmospheres. ZrO and TiO band strength indices as well as VJHKL photometry are needed to disentangle the effective temperature, C/O and [s/Fe]. The stellar parameters derived on the basis of low-resolution spectra and photometry are shown to be fairly accurate when compared to high-resolution data of the same stars. The C/O ratio of S stars is found to be between the solar value (0.5) and 0.99, and not 1 as often claimed in the literature. Consistently with stellar evolution expectations, the C/O ratio increases as the effective temperature decreases.