By using a new achiral phenylacetylene having bulky substituents as a monomer, living-like helix-sense-selective polymerization (HSSP) has been achieved. This is the first example of the HSSP of substituted acetylenes where the degree of polymerization was controlled. The resulting one-handed helical living polymer initiated polymerization of a second monomer to successfully yield a block copolymer. (C) 2013 Elsevier Ltd. All rights reserved.