Symmetry-breaking charge transfer upon photoexcitation of al inear A-p-D-p-A molecule (D and Ab eing electron donating and accepting groups) could be visualized using ultrafast time-resolved infrared spectroscopyb ym onitoring the CN stretching modes on the Aunits.W hereas in apolar solvents,the S 1 state remains symmetric and quadrupolar,s ymmetry breaking occurs within ca. 100 fs in polar solvents as shown by the presence of two CN bands,instead of one in apolar solvents,w ith as plitting that increases with polarity.I np rotic solvents,s ymmetry breaking is significantly amplified by H-bonding interactions,which are the strongest at the CN group with the highest basicity.I ns trongly protic solvents,the two CN bands transform in about 20 ps into new bands with al arger splitting,a nd the lifetime of the S 1 state is substantially reduced. This is attributed to the formation of an excited asymmetric tight H-bond complex.Scheme 1. Structure of ADA.Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under http://dx.