Colloidal sedimentation has been studied for decades from both thermodynamic and dynamic perspectives. In the present work, binary mixtures of colloidal spheres are observed to separate spontaneously into two distinct layers on sedimentation. Both layers have a high volume fraction and contain distinct compositions of particles. Although predicting these compositions using settling dynamics is challenging, here we show that the compositions are readily predicted thermodynamically by minimizing the gravitational energy of the system. As the random packing fraction of a mixture of spheres exceeds that of monodisperse spheres of either type, the mixture produces a denser suspension that forms the bottom phase. Experimentally, the use of charged particles and low-ionic-strength solutions provides interparticle repulsions that keep the packed particles mobile, avoiding a glassy state that would prevent particles from reaching their equilibrium configuration. We extend this work beyond binary systems, showing similar separated layers for a five-component mixture of particles.