Polymethoxylsiloxane (PMOS) with dense pendant silicone-methoxy groups was synthesized from cyclosiloxane monomers by ring-opening polymerization and dehydrocoupling reaction. Synthesis reactions were followed by IR spectroscopy and Si-29 NMR analyses. PMOS was used as crosslinking reagent for room temperature vulcanized polydimethylsiloxane (PDMS), and the apparent activation energy for crosslink reaction was 3.92 kJ/mol. TEM study shows that many dispersed high crosslink density PMOS phases were formed in siloxane elastomer as well as the PDMS networks, and the crosslink density increased from PDMS networks to PMOS phases gradually, without a clear interface. It was detected that these PMOS phases improved the thermal and mechanical properties of siloxane elastomer significantly because of their in-situ microscale improvement effect. TG analysis demonstrated that thermal decomposition process of PMOS crosslinked siloxane elastomer was divided into three stages, the second one corresponding to a possible loss of some new structures, and the residual mass at 500 degrees C was 66 wt %. The crosslink density went up as the loading of PMOS increased. Tensile stress and elastic module increased twice and three times, respectively, when the PMOS content increased from 15.1 to 41.6 wt %. (C) 2007 Wiley Periodicals, Inc.