The reversible helical pitch change of polyphenylacetylenes by a thermoresponsive rotaxane switch inserted into the side chain was demonstrated through an accompanying color change. Similar to an ethynyl rotaxane monomer, the corresponding polyphenylacetylene having a rotaxane moiety in its side chain exhibited a reversible helical pitch change induced by the thermoresponsive rotaxane switch, i.e., the amine/ammonium salt was converted by treatment with trichloroacetic acid (TCA) and subsequent heating, which led to thermal decomposition of TCA to chloroform and carbon dioxide. Such a rotaxane switch caused the helical pitch change and the accompanying color change of the polymer main chain in both solution and solid state.