This article deals with the onset of thermosolutal natural convection in horizontal superposed fluid and porous layers. A linear stability analysis is performed using the one-domain approach. As in the thermal convection case, the results show a bimodal nature of the marginal stability curves where each mode corresponds to a different convective instability. At small wave numbers, the convective flow occurs in the whole cavity ("porous mode") while perturbations of large wave numbers lead to a convective flow mainly confined in the fluid layer ("fluid mode"). Furthermore, it is shown that the onset of thermosolutal natural convection is characterized by a multi-cellular flow in the fluid region for negative thermal Rayleigh numbers. For positive thermal Rayleigh numbers, the convective flow takes place both in the fluid and porous regions. The influence of the depth ratio and thermal diffusivity ratio is also investigated for a wide range of the thermal Rayleigh numbers.