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Organocatalysts typically used for the ring-opening polymerization (ROP) of cyclic ester monomers are applied to a thiolactone, ε-thiocaprolactone (tCL). In the absence of an H-bond donor, a nucleophilic polymerization mechanism is proposed. Despite the decreased ability of thioesters and thiols (versus esters and alcohols) to H-bond, H-bonding organocatalysts—a thiourea in combination with an H-bond accepting base—are also effective for the ROP of tCL. The increased nucleophilicity of thiols (versus alcohols) is implicated in the increased Mw/Mn of the poly(thiocaprolactone) versus poly(caprolactone), but deleterious transesterification is suppressed in the presence of a thiourea. The thioester monomer, tCL, is shown to be thermodynamically similar to ε-caprolactam but kinetically similar to ε-caprolactone.