Population heterogeneity is ubiquitous among active living systems, but little is known about its role in determining their spatial organization and large-scale dynamics. Combining evidence from synthetic active fluids assembled from self-propelled colloidal particles along with theoretical predictions at the continuum scale, we demonstrate the spontaneous demixing of binary polar liquids within circular confinement. Our analysis reveals how both active speed heterogeneity and non-reciprocal repulsive interactions lead to self-sorting behavior. By establishing general principles for the self-organization of binary polar liquids, our findings highlight the specificity of multi-component active systems.