Communication: Stereospecific polymerizations of functionalized acetylenes were successfully performed using a Rh complex as the catalyst and triethylamine as a base yielding poly(3.4,5-tridodecyloxyphenylacetylene) (Poly5) and poly[3, 4, 5-tris((S)-3, 7-dimethyloctyloxy)phenylacetylene] (Poly6). PolyS and Poly6 are liquid crystalline with presumably a bilayer-type architecture in which the mesogens are arranged in an antiparallel overlapping interdigitated manner. Poly6 showed unusual thermal stereomutation in solution in a very narrow temperature range.