Although electron donor-acceptor complexes have been known for more than 70 years and are increasingly used in various applications, very little is still known about their structure in liquids. Here, we investigate the excited-state dynamics of a complex with two charge-transfer (CT) bands, which are usually discussed in terms of two distinct geometries, opening the possibility for photoselection. Apart from an initial ultrafast internal conversion to the lowest CT state upon high-energy band excitation, the ensuing dynamics do not depend on which CT transition has been excited, suggesting complexes of similar structures. The pure ground-state bleach dynamics, extracted using polarized transient absorption measurements, does not exhibit any hole-burning effect and is independent of the excitation wavelength, indicating an absence of photoselection. These results are rationalized using molecular dynamics simulations, which point to a broad distribution of structures with a significant oscillator strength for both transitions, contrary to the generally accepted picture.