The controlled synthesis of poly(dimethylsiloxane) homopolymers (PDMS) using hexamethyl(cyclotrisiloxane) monomer (D-3), a mixture of ciclohexane/tetrahydrofuran 50/50 v/v and sec-Bu-Li+ as initiator was studied using different experimental conditions, and whole-sealed glass reactors according to standards procedures in high-vacuum anionic polymerization. It was observed that polydispersity indexes (PD) and conversions strongly depend on temperature and reaction times. For PDMS homopolymers with molar masses below 100,000 g/mol, high conversion (>90%) and PD < 1.1 can be achieved at long reaction times (24 h) and mild temperature conditions (below or up to 30 degrees C). On the other hand, to synthesize PDMS homopolymers with molar masses higher than 100,000 g/mol and PD < 1.1 it is necessary to increase the temperature up to 50 degrees C and decrease the reaction time (8 h). However, under these reaction conditions, it was observed that the conversion decreases (about 65-70% conversion is achieved). Apparently, the competition between propagation and secondary reactions (redistribution, backbiting, and reshuffling) depends on the molar masses desired. According to the results obtained in this study-which were compared with others found in the scientific literature-propagation is favored when M-n < 100,000 g/mol, whereas secondary reactions seem to become important for higher molar masses. Nevertheless, model PDMS homopolymers with high molar masses can still be obtained increasing the reaction temperature and shortening the total reaction time. It seems that the combined effect of these two facts favors propagation against secondary reactions, and provides model PDMS homopolymers with molar masses quite close to the expected ones. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4774-4783, 2009