Electronic excitation in quadrupolar conjugated molecules rapidly localizes on a single electron donor–acceptor (DA) branch when in polar environments. The loss of center of inversion upon this excited-state symmetry breaking (ES-SB) can be monitored by exploiting the relaxation of the exclusion rules for IR and Raman vibrational transitions. Here, we compare ES-SB in a right-angled (1) and a centrosymmetric (2) DAD dyes using time-resolved IR spectroscopy. We show that the localization of the excitation can also be identified with the bent molecule 1. We find that contrary to dye 2, subpopulations with localized and delocalized excitation coexist for 1 in weak to medium polar solvents. This difference originates from the torsional disorder present in the excited state of 1 but not of 2. Additionally, irreversible localization in a bent molecule is shown to require higher solvent polarity than in a centrosymmetric one.