The miscibility condition for a binary mixture of two interacting Bose-Einstein condensates is shown to be deeply affected by interaction driven thermal fluctuations. These give rise to a first order phase transition to a demixed phase with full spatial separation of the two condensates, even if the mixture is miscible at zero temperature. Explicit predictions for the isothermal compressibility, the spin susceptibility, and the phase transition temperature T_{M} are obtained in the framework of Popov theory, which properly includes beyond mean-field quantum and thermal fluctuations in both the spin and density channels. For a mixture of two sodium condensates occupying the hyperfine states |F=1⟩,|m_{F}=1⟩ and |F=1,m_{F}=-1⟩, respectively, T_{M} is predicted to occur at about 0.7 times the usual BEC critical temperature.