The emissive properties of symmetric molecules containing several donor–acceptor branches are often similar to those of the single-branched analogues. This is due to the at least partial localization of the excitation on one branch. Detailed understanding of this excited-state symmetry breaking (ES-SB) requires the ability to monitor this process in real time. Over the past few years, several spectroscopic approaches were shown to enable visualization of ES-SB and of its dynamics. They include the detection of new vibrational or electronic absorption bands associated with transitions that are forbidden in the symmetric excited state. Alternatively, ES-SB can be detected by observing transitions that become weaker or vanish upon localization of the excitation. Herein, we discuss these different approaches as well as their merits and weaknesses.