A series of well-defined different chain lengths polymers, which contain the organometallic 1,3-dichloro-tetra-n-butyl-distannoxane core in the main chain, was obtained in one-pot via a novel 1,3-dichloro-tetra-n-butyl-distannoxane (complex A)/azobisisobutyronitrile (AIBN) initiating system used in reverse atom transfer radical polymerization of styrene in different concentrations. The introduction of organotin complex A was supported by H-1-NMR, C-13-NMR, and the Inductive Coupled Plasma Emission Spectrometer analysis of the organotin-containing polymer. Moreover, the mechanism of polymerization was investigated by changing the ratio of complex A to AIBN. It was concluded that the complex A not only acted as an important part of the initiator system but also introduced the functional organometallic group into the polymer chain. Additionally, the organotin-containing polymer could be used as catalyst for esterification, and the reaction products' conversion could reach high up to 99% and does not decrease after four successive cycles. (C) 2011 Wiley Periodicals, Inc. J Appl Polym Sci 123: 3485-3494, 2012