The developing urea class of H-bond donors facilitates the solvent-free ROP of lactones at ambient and elevated temperatures, displaying enhanced rates and control versus other known organocatalysts for ROP under solvent-free conditions. The ROPs retain the characteristics of living polymerizations despite solidifying prior to full conversion, and copolymers can be accessed in a variety of architectures. One-pot block copolymerizations of lactide and valerolactone, which had previously been inaccessible in solution phase organocatalytic ROP, can be achieved under these reaction conditions, and one-pot triblock copolymers are also synthesized. For the ROP of lactide, however, thioureas remain the more effective H-bond donating class. For all (thio)urea catalysts under solvent-free conditions and in solution, the more active catalysts are generally more controlled. A rationale for these observations is proposed. The triclocarban (TCC) plus base systems are particularly attractive in the context of solvent-free ROP due to their commercial availability which could facilitate the adoption of these catalysts.