An efficient synthetic pathway toward cyclic polymers based on the combination of thiolactone and disulfide chemistry, has been developed. First, heterotelechelic linear polystyrene (PS) containing an α-thiolactone (TLa) and an ω-dithiobenzoate group was synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization, employing a newly designed TLa-bearing chain transfer agent. The subsequent reaction of this heterotelechelic polymer with an amine, which acts as a nucleophile for both the TLa and dithiobenzoate units, generated the α,ω-thiol-telechelic PS under ambient conditions without the need for any catalyst or other additive. The arrangement of thiols under a high dilution afforded single cyclic c-PSs through an oxidative disulfide linkage. The cyclic polystyrene (c-PS) disulfide ring formation was evidenced by SEC, MALDI-TOF MS and 1 H-NMR characterization. Moreover, we demonstrated a controlled ring opening via either disulfide reduction or thiol/disulfide exchange to enable easy and clean topology transformation. Furthermore, to illustrate the broad utility of this synthetic methodology, different amines including functional ones were employed, allowing for the one-step preparation of functionalized cyclic polymers with high yields.