C343, a common molecular probe utilized in solvation dynamics experiments, was studied in homogeneous media. Absorption, emission, and (HNMR)-H-1 spectroscopies were used to investigate the behavior of C343 in benzene and in benzene/n-heptane mixtures. We demonstrate the implications of the medium polarity, measured as the Kamlet-Taft polarity-polarizability (pi*) parameter, in the C343 inter/intramolecular hydrogen bond (H-bond) interactions and the role that this interaction plays in the dimerization process of the dye. In pure benzene, the dimer prevails because the intermolecular H-bond interaction is favored. On the other hand, as the n-heptane content increases the intramolecular H-bond is the strongest and the C343 monomer is favored. As the polarity of the medium decreases, the solvophobic interaction makes that C343 monomer species experiences a more complicated aggregation process beyond the simple monomer dimer equilibrium present in pure benzene. Thus, the addition of n-heptane to the mixture yields a C343 higher-order aggregates species. Thus, our work reveals the importance that the medium has on the behavior of a widespread dye used as chromophore for very different systems such as homogeneous and microheterogenous media. This is very important since the use of chromophores without understanding its chemistry can induce artifacts into the interpretation of solvation dynamics in heterogeneous environments, in particular, those provided by biological systems such as proteins. Considerable care in choosing and characterizing the system is required to analyze the results fully.