Natural products (NPs) constitute a significant source of active biomolecules widely used in medicine, pharmacology and cosmetics. However, NPs structural characterization has the drawback of their chemical instability during the extraction steps and their likely transformation during the analytical protocol. In particular, tamariscol and conocephalenol are two compounds largely used in the cosmetic industry for their odorant properties. Thus, in the present study, we focused on the evolution of these two metabolites (extracted from Frullania tamarisci and Conocephalum conicum, respectively), as followed by NMR. Interestingly, we found that, once dissolved in deuterated chloroform, these two tertiary alcohols are both subjected to transformation processes, leading to degradation compounds with altered structures. Accordingly, these detected degradation compounds have been fully characterized by NMR and the experimental findings were supported by computational chemistry data.