H-bonding organocatalysis using (thio) urea/amine achieved massive success. H-bonding binding with Bronsted acid catalysis, especially in polymerizations, was scarcely explored. Here we disclosed 1,3-bis-(3,5-bis(trifluoromethyl) phenyl) thiourea (TU) as hydrogen bond donor (HBD), combined with trifluoroacetic acid (TFA) as a Bronsted acid (BA), promoted efficient controlled/living ring-opening polymerization (ROP) of delta-valerolactone (delta-VL) and epsilon-caprolactone (epsilon-CL) at room temperature. The ROPs of delta-VL and epsilon-CL with benzyl alcohol (BnOH) as the initiator yielded poly(delta-valerolactone) (PVL, M-n,M-NMR = 1900-9900 g mol(-1), M-w/M-n = 1.28-1.34) and poly(epsilon-caprolactone) (PCL, M-n,M- NMR = 2400 - 11,600 g mol(-1), M-w/M-n = 1.19-1.35) with predicted molecular weights and narrow dispersities. A plausible mechanism of the ROP promoted by associations of TU with TFA through double hydrogen bonding was suggested, in which stabilizing of the carboxylate anion and enhancing of the Bronsted acidity made the catalytic ROPs by TU-TFA viable. The quantitative incorporation of the initiator into the polymer chains was demonstrated by H-1 NMR and MALDI-ToF MS measurements. The controlled/living fashion of the polymerization was supported by the kinetics and chain extension experiments. Synthesis of well defined block copolymers of PVL-b-PCL and PCL-b-PVL verified again the ROPs were in controlled/living manner, and suggested the hydrogen bond donor binding with Bronsted acid catalysis to be a generally applicable method. (C) 2016 Elsevier Ltd. All rights reserved.