Hydroxyl chain-end functionalizations of polymeric organolithium compounds with oxetane (trimethylene oxide) were studied in benzene at 25 degrees C. Functionalizations of poly(styryl)lithium and polystyrene-oligo-butadienyllithium proceed efficiently to form the corresponding omega-hydroxypropyl-functionalized polymers in 98 and 97% isolated yields, respectively. No nonfunctional polymer (<= 1-2%) was detected by thin layer chromatography (TLC) analysis for either polymer. All functionalized polymers were characterized by C-13 and H-1 NMR analyses; no evidence for oxetane oligomerization at the chain end was observed. The MALDI-TOF mass spectrum of omega-hydroxypropylpolystyrene was consistent with the expected structure without any detectable oligomerization of oxetane. A small, but detectable series of peaks corresponding to nonfunctional polystyrene was also observed in the MALDI-TOF mass spectrum. The functionalization of the adduct of 1,1-dipbenylethylene and PSLi produced the corresponding omega-hydroxypropyl-functionalized polymer in only 86% isolated yield. (c) 2006 Wiley Periodicals, Inc.