The radical polymerizations of 2-, 3-, and 4-(trimethylsilylethynyl)styrenes (1a-c) and copolymerizations of 1a-c (M-1) with styrene (M-2) have been studied. Copolymerization parameters were determined as r(1) = 1.22 and r(2) = 0.54 for 1a, r(1) = 1.10 and r(2) = 0.90 for 1b, and r(1) = 1.42 and r(2) = 0.38 for 1c. The deprotection of the trimethylsilyl groups in poly[(trimethylsilylethynyl)styrene] (2a-c) and poly [(trimethylsilylethynyl) styrene-co-styrene] (4a-c) using (C4H9)(4)NF smoothly proceeded to yield poly(ethynylstyrene) (3a-c) and poly(ethynylstyrene-co-styrene) (5a-c), respectively, which underwent curing reactions at elevated temperature to form crosslinking polystyrenes.