Upon photoexcitation, a majority of quadrupolar dyes, developed for large two-photon absorption, undergo excited-state symmetry breaking (ES-SB) and behave as dipolar molecules. We investigate how the change of quadrupole moment upon S 1  <- S 0  excitation, ? Q , influences the propensity of a dye to undergo ES-SB using a series of molecules with a A -π- D -π- A motif where D is the exceptionally electron-rich pyrrolo[3,2-b]pyrrole and A are accepting groups. Tuning of ? Q is achieved by appending a secondary acceptor group, A? , on both sides of the D core and ES-SB is monitored using a combination of time-resolved IR and broadband fluorescence spectroscopy. The results reveal a clear correlation between ? Q and the tendency to undergo ES-SB. When A is a stronger acceptor than A? , ES-SB occurs already in non-dipolar but quadrupolar solvents. When A and A? are identical, ES-SB is only partial even in highly dipolar solvents. When A is a weaker acceptor than A? , the orientation of ? Q changes, ES-SB is observed in dipolar solvents only and involves major redistribution of the excitation over the D -π- A  and D - A? branches of the dye.