Methyl-tri(phenylethynyl)silane (MTPES) was successfully synthesized by the reaction of lithium phenylacetylide with methyltrichlorosilane. The structure was characterized by HRMS, FTIR, Si-NMR, and elementary analysis. Thermal cure process was monitored by DSC, DMA, and FTIR. MTPES was heated to free flowing liquid around 1308C and thermally polymerized at 327-3778C to form thermoset. Thermal and oxidative properties were evaluated by TGA analysis. Thermoset exhibits extremely high heat-resistance and TGA curve in nitrogen shows the temperature of 5% weight loss (Td 5 ) of 6958C and total weight loss at 8008C of 7.1%. TGA shows a high Td 5 of 5658C even in air, although the total weight loss at 8008C was 56.1% of the initial weight, much higher than that in nitrogen. The high heat resistance of MTPES was ascribed to crosslinking reaction concerning ethynyl groups. Aging studies performed at elevated temperatures in air on a thermoset showed that MTPES is oxidatively stable to 3008C.