In this Letter, I report on a novel scheme for beam stacking without any beam emittance dilution using a barrier rf system in synchrotrons. The general principle of the scheme called longitudinal phase-space coating, validation of the concept via multi-particle beam dynamics simulations applied to the Fermilab Recycler, and its experimental demonstration are presented. In addition, it has been shown and illustrated that the rf gymnastics involved in this scheme can be used in measuring the incoherent synchrotron tune spectrum of the beam in barrier buckets and in producing a clean hollow beam in longitudinal phase space. The method of beam stacking in synchrotrons presented here is the first of its kind.