An isotropic melt of a chiral side‐chain polymethacrylate was studied by electric birefringence technique. A phase transition between two different isotropic phases was detected by Kerr effect and confirmed by WAXS measurements. The obtained experimental data can explain the previously reported bistable phase behavior of the polymer, as conventional Sm A phase is formed in slow cooling whereas a TGB‐like, optically isotropic mesophase in fast cooling.magnified image